U.S. patent application number 14/310484 was filed with the patent office on 2015-12-24 for carrier fluid compounds and dye compounds for electrowetting apparatus.
The applicant listed for this patent is Amazon Technologies, Inc.. Invention is credited to Robin Leguijt, Jurrin.degree.n Mans, Sukhdip Sandhu.
Application Number | 20150370062 14/310484 |
Document ID | / |
Family ID | 53539651 |
Filed Date | 2015-12-24 |
United States Patent
Application |
20150370062 |
Kind Code |
A1 |
Leguijt; Robin ; et
al. |
December 24, 2015 |
CARRIER FLUID COMPOUNDS AND DYE COMPOUNDS FOR ELECTROWETTING
APPARATUS
Abstract
Electrowetting apparatus including at least one compound
selected from the group consisting of: ##STR00001## wherein each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently an alkyl
group. In examples a fluid includes a dye compound selected from:
##STR00002##
Inventors: |
Leguijt; Robin; (Eindhoven,
NL) ; Mans; Jurrin.degree.n; (Eindhoven, NL) ;
Sandhu; Sukhdip; (Eindhoven, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Amazon Technologies, Inc. |
Reno |
NV |
US |
|
|
Family ID: |
53539651 |
Appl. No.: |
14/310484 |
Filed: |
June 20, 2014 |
Current U.S.
Class: |
359/290 ;
252/500; 534/573; 556/465; 556/87 |
Current CPC
Class: |
G02B 26/005 20130101;
C09B 29/081 20130101; C09B 1/262 20130101; C09B 29/0003 20130101;
C09B 31/14 20130101; C09B 55/009 20130101; C09B 56/08 20130101;
C09B 31/18 20130101; C09B 13/02 20130101; C09B 31/043 20130101;
C09B 1/26 20130101; C07F 7/0805 20130101; C07F 7/30 20130101 |
International
Class: |
G02B 26/00 20060101
G02B026/00; C07F 7/08 20060101 C07F007/08; C07F 7/30 20060101
C07F007/30 |
Claims
1. Electrowetting apparatus including at least one compound
selected from the group consisting of: ##STR00071## wherein each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently an alkyl
group.
2. Electrowetting apparatus according to claim 1, wherein the alkyl
group of each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is
independently a straight chain alkyl group having the general
formula --(CH.sub.2).sub.nCH.sub.3 and n is independently, for each
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4, in the range of 0 to
7
3. Electrowetting apparatus according to claim 2, wherein a number
of carbon atoms contained by each of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 is the same.
4. Electrowetting apparatus according to claim 3, wherein the at
least one compound includes one or more of the following:
##STR00072##
5. Electrowetting apparatus according to claim 2, wherein a number
of carbon atoms contained by one or more of: R.sup.1, R.sup.2,
R.sup.3 or R.sup.4 is different from a number of carbon atoms
contained by a different one of: R.sup.1, R.sup.2, R.sup.3 or
R.sup.4.
6. Electrowetting apparatus according to claim 5, wherein the at
least one compound includes the following: ##STR00073##
7. Electrowetting apparatus according to claim 1, wherein one of
the following applies: each of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 is independently a branched alkyl group, or each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently a straight
chain alkyl group.
8. Electrowetting apparatus according to claim 1, wherein a total
number of carbon atoms contained by all of the alkyl groups
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is at most 33 carbon
atoms.
9. Electrowetting apparatus according to claim 1, wherein a total
number of carbon atoms contained by any one of the alkyl groups
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is at most 30.
10. Electrowetting apparatus according to claim 1, wherein a
longest chain of carbon atoms contained by the alkyl group of any
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is at most 24 carbon
atoms.
11. Electrowetting apparatus according to claim 1, wherein the
alkyl group of each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is a
saturated alkyl group.
12. Electrowetting apparatus according to claim 1, wherein a
maximum vapour pressure of said at least one compound is about 5
millimetres Hg measured at a temperature of 20 degrees Celsius.
13. Electrowetting apparatus according to claim 1, wherein a
dynamic viscosity of said at least one compound is at most about 37
centiPoise measured at a temperature of 20 degrees Celsius.
14. Electrowetting apparatus according to claim 1, wherein a
dynamic viscosity of said at least one compound is in the range of
one or more of: about 0.5 to 37 centiPoise, about 0.5 to 35
centiPoise, about 0.5 to 30 centiPoise, about 0.5 to 25 centiPoise,
about 0.5 to 20 centiPoise, about 0.5 to 15 centiPoise, about 0.5
to 10 centiPoise, about 0.5 to 9 centiPoise, about 0.5 to 8
centiPoise, about 0.5 to 7 centiPoise, about 0.5 to 6 centiPoise,
about 0.5 to 5.5 centiPoise, about 0.5 to 5.0 centiPoise, about 0.5
to 4.5 centiPoise, about 0.5 to 4.0 centiPoise, about 0.5 to 3.5
centiPoise, or about 0.5 to 3.0 centiPoise, measured at a
temperature of 20 degrees Celsius.
15. Electrowetting apparatus according to claim 1, comprising a
fluid including said at least one compound.
16. Electrowetting apparatus according to claim 1, comprising at
least one electrowetting display element including: a first support
plate; a second support plate; a first fluid comprising said at
least one compound; a second fluid immiscible with the first fluid,
the first and second fluids being positioned between the first and
second support plates; and at least one electrode arranged in one
or more of said first or second support plates for applying a
voltage to control a configuration of the first and second
fluid.
17. A fluid for an electrowetting apparatus, the fluid including a
carrier fluid for at least one of a dye compound and a pigment, the
carrier fluid comprising at least one compound selected from the
group consisting of: ##STR00074## wherein each of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 is independently an alkyl group.
18. A fluid according to claim 17, wherein the alkyl group of each
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently a
straight chain alkyl group having the general formula
--(CH.sub.2).sub.nCH.sub.3 and n is independently, for each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4, in the range of 0 to 7
19. A fluid according to claim 18, wherein a number of carbon atoms
contained by each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is the
same.
20. A fluid according to claim 19, wherein the at least one
compound includes one or more of the following: ##STR00075##
21. A fluid according to claim 18, wherein a number of carbon atoms
contained by one or more of: R.sup.1, R.sup.2, R.sup.3 or R.sup.4
is different from a number of carbon atoms contained by a different
one of: R.sup.1, R.sup.2, R.sup.3 or R.sup.4.
22. A fluid according to claim 21, wherein the at least one
compound includes the following: ##STR00076##
23. A fluid according to claim 17, wherein a total number of carbon
atoms contained by all of the alkyl groups R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 is at most 33 carbon atoms.
24. A fluid according to claim 17, wherein a total number of carbon
atoms contained by any one of the alkyl groups R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 is at most 30.
25. A fluid according to claim 17, wherein a longest chain of
carbon atoms contained by the alkyl group of any of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 is at most 24 carbon atoms.
26. A fluid according to claim 17, wherein the carrier fluid
includes at least one dye compound at least partly dissolved
therein, the dye compound being selected from the group consisting
of: ##STR00077## where R.sup.5 is H; R.sup.6 is an alkoxy group
having the formula --O--R.sup.a, wherein R.sup.a is one of: an
alkyl group or a haloalkyl group; R.sup.7 is selected from: an
amino group having the formula --N(R.sup.b)(R.sup.c), wherein each
of R.sup.b and R.sup.c is an alkyl group, or --N.dbd.N--Het.sup.1
where Het.sup.1 is a heterocyclic group; R.sup.8 is H; R.sup.9 is
selected from: an alkoxy group having the formula --O--R.sup.d,
wherein R.sup.d is an alkyl group; an amide group having the
formula --NHC(.dbd.O)R.sup.e, wherein R.sup.e is an alkyl group; a
sulphonamide group having the formula
--NH--S(.dbd.O)(.dbd.O)R.sup.f, wherein R.sup.f is an alkyl group,
or an amidophosphate group having the formula
--NH--P(.dbd.O)(OR.sup.g).sub.2, wherein R.sup.g is independently
an alkyl group, R.sup.10 has the formula B-A-, where B has the
formula: ##STR00078## wherein R.sup.H is H; R.sup.12 is selected
from: H, a cyano group having the formula --CN, an alkoxy group
having the formula --O--R.sup.h, wherein R.sup.h is an alkyl group,
an alkyl group or a halogen atom; R.sup.13 is selected from: H, a
cyano group having the formula --CN, an alkyl group R.sup.j, or a
halogen atom; R.sup.14 is selected from: H, a cyano group having
the formula --CN, a nitro group having the formula --NO.sub.2, or
an alkoxy group having the formula --O--R.sup.k, wherein R.sup.k is
an alkyl group; R.sup.15 is selected from: a cyano group having the
formula --CN, a nitro group having the formula --NO.sub.2, an ester
group having the formula --COO--R.sup.1, wherein R.sup.1 is an
alkyl group, an alkoxy group having the formula --O--R.sup.m,
wherein R.sup.m is an alkyl group, an alkyl group R.sup.n, a
halogen atom, or a sulphonyl group having the formula --SOOOH;
wherein A is selected from: a single bond, a formula selected from
the group consisting of: ##STR00079## wherein R.sup.16 is H;
R.sup.17 is selected from: H, or an alkoxy group having the formula
--O--R.sup.o, wherein R.sup.o is an alkyl group; R.sup.18 is H;
R.sup.19 is selected from: H, or an alkoxy group having the formula
--O--R.sup.p, wherein R.sup.p is an alkyl group; ##STR00080##
wherein R.sup.30 is selected from: OH, or an amino group having the
formula --N(R.sup.q)(R.sup.r), wherein R.sup.q is H and R.sup.r is
an alkyl group; an alkoxy group having the formula --O--R.sup.ae,
wherein R.sup.ae is an alkyl group; or a thioalkyl group having the
formula --S--R.sup.af, wherein R.sup.af is an alkyl group, R.sup.31
is selected from: H, or has the formula --X--Y, wherein X is
selected from: --S--, a single bond, or --O--; Y is selected from:
--R.sup.s, or --R.sup.A, wherein R.sup.s is an alkyl group and
R.sup.A is an aryl group; R.sup.32 is H; R.sup.33 is selected from:
an amino group having the formula --N(R.sup.t)(R.sup.u), wherein
R.sup.t is H and R.sup.o is an alkyl group, an alkoxy group having
the formula --O--R.sup.af, wherein R.sup.af is an alkyl group, or a
thioalkyl group having the formula --S--R.sup.ag, wherein R.sup.ag
is an alkyl group; R.sup.34 and R.sup.35 are selected from the
following: R.sup.34 and R.sup.35 are each H, or together R.sup.34
and R.sup.35 form: ##STR00081## where R.sup.36, R.sup.38 and
R.sup.39 are each independently selected from: H, or an alkyl
group; R.sup.37 is selected from: H, an alkyl group, or an ester
group having the formula --COO--R.sup.ah, where R.sup.ah is an
alkyl group; ##STR00082## wherein each of R.sup.40, R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46 is independently
selected from: H, an alkoxy group, an alkyl group, or an amino
group having the formula --N(R.sup.v)(R.sup.w), wherein R.sup.v is
H and R.sup.w is one of: H, or an alkyl group; where R.sup.47 is an
arylene group and R.sup.48 is an aryl group; ##STR00083## wherein
R.sup.50 and R.sup.51 are independently selected from: H, or an
amide group having the formula --NH--C(.dbd.O)R.sup.aj wherein
R.sup.aj is selected from H, or an alkyl group, or together
R.sup.50 and R.sup.51 form: ##STR00084## wherein each of R.sup.60,
R.sup.61, R.sup.62, R.sup.63 is independently H or an alkyl group;
R.sup.53 and R.sup.54 are selected from the following: R.sup.53 and
R.sup.54 are each H, or together R.sup.53 and R.sup.54 form:
##STR00085## wherein each of R.sup.64, R.sup.65, R.sup.66, R.sup.67
is independently H or an alkyl group; R.sup.52 has the formula:
##STR00086## wherein R.sup.55 is selected from: an alkoxy group
having the formula --O--R.sup.x, wherein R.sup.x is an alkyl group,
an alkyl group, or a halogen atom; R.sup.57 is an amino group
having the formula --N(R.sup.y)(R.sup.z), wherein each of R.sup.y
and R.sup.z independently is selected from: H, or an alkyl group;
each of R.sup.56, R.sup.58 and R.sup.59 is independently selected
from: H, or an alkyl group.
27. A fluid for an electrowetting apparatus, the fluid including at
least one dye compound selected from: ##STR00087## wherein R.sup.5
is H; R.sup.6 is an alkoxy group having the formula --O--R.sup.a,
wherein R.sup.a is an alkyl group; R.sup.7 is selected from: an
amino group having the formula --N(R.sup.b)(R.sup.c), wherein each
of R.sup.b and R.sup.c is an alkyl group, or --N.dbd.N--Het.sup.1
wherein Het.sup.1 is a heterocyclic group; R.sup.8 is H; R.sup.9 is
selected from: an alkoxy group having the formula --O--R.sup.d,
wherein R.sup.d is an alkyl group; an amide group having the
formula --NHC(.dbd.O)R.sup.e, wherein R.sup.e is an alkyl group; a
sulphonamide group having the formula
--NH--S(.dbd.O)(.dbd.O)--R.sup.f, wherein R.sup.f is an alkyl
group, or an amidophosphate group having the formula
--NH--P(.dbd.O)(--O--R.sup.g).sub.2, wherein R.sup.g is
independently an alkyl group, R.sup.10 has the formula B-A-,
wherein B has the formula: ##STR00088## wherein R.sup.11 is H;
R.sup.12 is selected from: H, a cyano group having the formula
--CN, an alkoxy group having the formula --O--R.sup.h, wherein
R.sup.h is an alkyl group, an alkyl group or a halogen atom;
R.sup.13 is selected from: H, a cyano group having the formula
--CN, an alkyl group R.sup.j, or a halogen atom; R.sup.14 is
selected from: H, a cyano group having the formula --CN, a nitro
group having the formula --NO.sub.2, or an alkoxy group having the
formula --O--R.sup.k, wherein R.sup.k is an alkyl group; R.sup.15
is selected from: a cyano group having the formula --CN, a nitro
group having the formula --NO.sub.2, an ester group having the
formula --COO--R.sup.l, wherein R.sup.l is an alkyl group, an
alkoxy group having the formula --O--R.sup.m, wherein R.sup.m is an
alkyl group, an alkyl group R.sup.n, a halogen atom, or a sulphonyl
group having the formula --SOOOH; wherein A is selected from: a
single bond, a formula selected from the group consisting of:
##STR00089## where R.sup.16 is H; R.sup.17 is selected from: H, or
an alkoxy group having the formula --O--R.sup.o, wherein R.sup.o is
an alkyl group; R.sup.18 is H; R.sup.19 is selected from: H, or an
alkoxy group having the formula --O--R.sup.p, wherein R.sup.p is an
alkyl group; ##STR00090## wherein R.sup.30 is selected from: OH, or
an amino group having the formula --N(R.sup.q)(R.sup.r), wherein
R.sup.q is H and R.sup.r is an alkyl group; an alkoxy group having
the formula --O--R.sup.ae, wherein R.sup.ae is an alkyl group; or a
thioalkyl group having the formula --S--R.sup.af, wherein R.sup.af
is an alkyl group, R.sup.31 is selected from: H, or has the formula
--X--Y, wherein X is selected from: --S--, a single bond, or --O--;
Y is selected from: --R.sup.s, or --R.sup.A, wherein R.sup.s is an
alkyl group and R.sup.A is an aryl group; R.sup.32 is H; R.sup.33
is selected from: an amino group having the formula
--N(R.sup.t)(R.sup.u), wherein R.sup.t is H and R.sup.u is an alkyl
group, an alkoxy group having the formula --O--R.sup.af, wherein
R.sup.af is an alkyl group, or a thioalkyl group having the formula
--S--R.sup.ag, wherein R.sup.ag is an alkyl group; R.sup.34 and
R.sup.35 are selected from the following: R.sup.34 and R.sup.35 are
each H, or together R.sup.34 and R.sup.35 form: ##STR00091##
wherein R.sup.36, R.sup.38 and R.sup.39 are each independently
selected from: H, or an alkyl group; R.sup.37 is selected from: H,
an alkyl group, or an ester group having the formula
--COO--R.sup.ah, wherein R.sup.ah is an alkyl group; ##STR00092##
wherein each of R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45, R.sup.46 is independently selected from: H, an alkoxy
group, an alkyl group, or an amino group having the formula
--N(R.sup.v)(R.sup.w), wherein R.sup.v is H and R.sup.w is one of:
H, or an alkyl group; wherein R.sup.47 is an arylene group and
R.sup.48 is an aryl group; ##STR00093## wherein R.sup.50 and
R.sup.51 are independently selected from: H, or an amide group
having the formula --NH--C(.dbd.O)R.sup.aj wherein R.sup.aj is
selected from H, or an alkyl group, or together R.sup.50 and
R.sup.51 form: ##STR00094## wherein each of R.sup.60, R.sup.61,
R.sup.62, R.sup.63 is independently H or an alkyl group; R.sup.53
and R.sup.54 are selected from the following: R.sup.53 and R.sup.54
are each H, or together R.sup.53 and R.sup.54 form: ##STR00095##
wherein each of R.sup.64, R.sup.65, R.sup.66, R.sup.67 is
independently H or an alkyl group; R.sup.52 has the formula:
##STR00096## wherein R.sup.55 is selected from: an alkoxy group
having the formula --O--R.sup.x, wherein R.sup.x is an alkyl group,
an alkyl group, or a halogen atom; R.sup.57 is an amino group
having the formula --N(R.sup.y)(R.sup.z), wherein each of R.sup.y
and R.sup.z independently is selected from: H, or an alkyl group;
each of R.sup.56, R.sup.58 and R.sup.59 is independently selected
from: H, or an alkyl group.
28. A fluid according to claim 27, wherein the alkyl group of one
or more of: R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f,
R.sup.g, R.sup.h, R.sup.k, R.sup.l, R.sup.m, R.sup.n, R.sup.o,
R.sup.p, R.sup.r, R.sup.ae, R.sup.af, R.sup.s, R.sup.u, R.sup.af,
R.sup.ag, R.sup.36, R.sup.38, R.sup.39, R.sup.37, R.sup.ah,
R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45,
R.sup.46, R.sup.y, R.sup.w, R.sup.aj, R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67, R.sup.x,
R.sup.55, R.sup.y, R.sup.z, R.sup.56, R.sup.58, or R.sup.59 is
independently selected from: a straight chain alkyl group having 1
to 22 carbon atoms, a branched alkyl group having 3 to 22 carbon
atoms, or a cyclic alkyl group having 5 to 22 carbon atoms.
29. A fluid according to claim 27, including the dye compound
according to Formula 1, wherein R.sup.a is selected from: a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a branched alkyl group such that R.sup.6 has the
formula: ##STR00097##
30. A fluid according to claim 27, including the dye compound
according to Formula 1, wherein where R.sup.7 is the amino group
having the formula --N(R.sup.b)(R.sup.c), the alkyl group of
R.sup.b and R.sup.c are each independently selected from: a
straight chain alkyl group having 1 to 22 carbon atoms, a straight
chain alkyl group having 1 to 8 carbon atoms, a straight chain
alkyl group having 8 carbon atoms, a straight chain alkyl group
having 6 carbon atoms, a straight chain alkyl group having 1 to 5
carbon atoms, a straight chain alkyl group having 5 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, a branched alkyl group such that the amino group of
R.sup.7 has the formula: ##STR00098## a straight chain alkyl group
having 5 carbon atoms, or a straight chain alkyl group having 4
carbon atoms.
31. A fluid according to claim 27, including the dye compound
according to Formula 1, wherein R.sup.7 is --N.dbd.N--Het.sup.1
where Het.sup.1 is a heterocyclic group selected from: a five
membered heterocyclic ring, a six membered heterocyclic ring, a
five membered heterocyclic aromatic ring containing 1 to 3
heteroatoms, a six membered heterocyclic aromatic ring containing 1
to 3 heteroatoms, a five membered heterocyclic aromatic ring
containing 1 heteroatom which is an N atom, a six membered
heterocyclic aromatic ring containing 1 heteroatom which is an N
atom, a five membered heterocyclic aromatic ring containing 1
heteroatom which is an N atom, where the --N.dbd.N-- group is
bonded to the heterocyclic aromatic ring at the 2 position relative
to the heteroatom, a six membered heterocyclic aromatic ring
containing 1 heteroatom which is an N atom, where the --N.dbd.N--
group is bonded to the heterocyclic aromatic ring at the 2
position, a five membered heterocyclic aromatic ring containing 1
heteroatom substituted with an alkyl group having 1 to 22 carbon
atoms, a five membered heterocyclic aromatic ring containing 1
heteroatom substituted with a straight chain alkyl group having 1
to 22 carbon atoms, a five membered heterocyclic aromatic ring
containing 1 heteroatom substituted with a straight chain alkyl
group having 1 to 8 carbon atoms, a five membered heterocyclic
aromatic ring containing 1 heteroatom substituted with a straight
chain alkyl group having 8 carbon atoms, a five membered
heterocyclic aromatic ring containing 1 heteroatom substituted with
a branched alkyl group having 3 to 22 carbon atoms, a five membered
heterocyclic aromatic ring containing 1 heteroatom substituted with
a branched alkyl group having 3 to 8 carbon atoms, a five membered
heterocyclic aromatic ring containing 1 heteroatom substituted with
a branched alkyl group having 8 carbon atoms, or a five membered
heterocyclic aromatic ring containing 1 heteroatom substituted with
a branched alkyl group having the formula: ##STR00099## a six
membered heterocyclic aromatic ring containing 1 heteroatom
substituted with an alkyl group having 1 to 22 carbon atoms, a six
membered heterocyclic aromatic ring containing 1 heteroatom
substituted with a straight chain alkyl group having 1 to 22 carbon
atoms, a six membered heterocyclic aromatic ring containing 1
heteroatom substituted with a straight chain alkyl group having 1
to 8 carbon atoms, a six membered heterocyclic aromatic ring
containing 1 heteroatom substituted with a straight chain alkyl
group having 8 carbon atoms, a six membered heterocyclic aromatic
ring containing 1 heteroatom substituted with a branched alkyl
group having 3 to 22 carbon atoms, a six membered heterocyclic
aromatic ring containing 1 heteroatom substituted with a branched
alkyl group having 3 to 8 carbon atoms, a six membered heterocyclic
aromatic ring containing 1 heteroatom substituted with a branched
alkyl group having 8 carbon atoms, or a six membered heterocyclic
aromatic ring containing 1 heteroatom substituted with a branched
alkyl group having the formula: ##STR00100## or a five membered
heterocyclic aromatic ring having the formula: ##STR00101##
32. A fluid according to claim 27, including the dye compound
according to Formula 1, wherein one or more of the following apply:
the alkyl group of R.sup.d is selected from: a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group such that the alkoxy group of R.sup.9 has the
formula: ##STR00102## or the alkyl group of R.sup.e is selected
from: a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 7 carbon atoms, a branched alkyl
group having 7 carbon atoms, or a branched alkyl group such that
the amide group of R.sup.9 has the formula: ##STR00103## or the
alkyl group of R.sup.f is selected from: a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group having the formula: ##STR00104## or the alkyl
group of R.sup.g is selected from: a straight chain alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 2
carbon atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00105##
33. A fluid according to claim 27, including the dye compound
according to Formula 1, wherein B has a formula selected from: a
formula where R.sup.12 is a cyano group having the formula --CN,
R.sup.13 is H, R.sup.14 is H and R.sup.15 is a cyano group having
the formula --CN, a formula wherein R.sup.12 is H, R.sup.13 is H,
R.sup.14 is H and R.sup.15 is a cyano group having the formula
--CN, a formula wherein: R.sup.12 is an alkoxy group having the
formula --O--R.sup.h wherein R.sup.h is an alkyl group selected
from: a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00106## R.sup.13 is H, R.sup.14 is an alkoxy group
having the formula --O--R.sup.k wherein R.sup.k is an alkyl group
selected from: a branched alkyl group having 3 to 22 carbon atoms,
a branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00107## R.sup.15 is a nitro group having the formula
--NO.sub.2.
34. A fluid according to claim 32, wherein A is selected from: a
single bond, or where A has a formula selected from the group
consisting of: ##STR00108## R.sup.o and R.sup.p are independently
selected from: a branched alkyl group having 3 to 22 carbon atoms,
a branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00109##
35. A fluid according to claim 27, including a dye compound
according to Formula 1 selected from: ##STR00110## ##STR00111##
##STR00112## ##STR00113##
36. A fluid according to claim 27, including a dye compound
according to Formula 2 selected from: a formula wherein: R.sup.30
is OH, R.sup.31 has the formula --X--Y wherein X is a single bond
and Y is --R.sup.s where --R.sup.s is selected from: an alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 22 carbon atoms, a straight chain alkyl group having 1 to 8
carbon atoms, a straight chain alkyl group having 8 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a branched alkyl group having the formula:
##STR00114## R.sup.33 is the amino group having the formula
--N(R.sup.t)(R.sup.u), wherein R.sup.t is H and R.sup.u is an alkyl
group selected from: an alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 22 carbon atoms, a straight
chain alkyl group having 1 to 8 carbon atoms, a straight chain
alkyl group having 8 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, a branched alkyl group having 3 to 8 carbon
atoms, a branched alkyl group having 8 carbon atoms, or a branched
alkyl group having the formula: ##STR00115## R.sup.34 and R.sup.35
together form: ##STR00116## wherein R.sup.36, R.sup.37, R.sup.38
and R.sup.39 are each H, or a formula wherein: R.sup.30 is the
amino group having the formula --N(R.sup.q)(R.sup.r), wherein
R.sup.q is H and R.sup.r is an alkyl group selected from: an alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 8 carbon atoms, a straight chain alkyl group having 8 carbon
atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a methyl alkyl group; R.sup.31 has
the formula --X--Y where X is --S-- and Y is R.sup.s being an alkyl
group selected from: an alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 22 carbon atoms, a straight
chain alkyl group having 1 to 12 carbon atoms, a straight chain
alkyl group having 12 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, a branched alkyl group having 3 to 12 carbon
atoms, a branched alkyl group having 12 carbon atoms, or a branched
alkyl group having the formula: ##STR00117## R.sup.33 is the amino
group having the formula --N(R.sup.t)(R.sup.u), wherein R.sup.t is
H and R.sup.u is an alkyl group selected from: an alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 22 carbon atoms, a straight chain alkyl group having 1 to 8
carbon atoms, a straight chain alkyl group having 8 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a branched alkyl group having the formula:
##STR00118## R.sup.34 and R.sup.35 together form: ##STR00119##
where R.sup.36, R.sup.37, R.sup.38 and R.sup.39 are each H.
37. A fluid according to claim 27, including a dye compound
according to Formula 2 selected from: ##STR00120##
38. A fluid according to claim 27, including a dye compound
according to Formula 3, wherein R.sup.40, R.sup.41, R.sup.42,
R.sup.43, R.sup.44, R.sup.45, R.sup.46 are each independently
selected from: H, a straight chain alkyl group having 1 to 22
carbon atoms, a branched alkyl group having 3 to 22 carbon atoms,
or an amino group having the formula --N(R.sup.v)(R.sup.w), wherein
R.sup.v is H and R.sup.w is one of: H, or an alkyl group selected
from: a straight chain alkyl group having 1 to 22 carbon atoms, or
a branched alkyl group having 3 to 22 carbon atoms; R.sup.47 has
the formula: ##STR00121## wherein each of R.sup.am, R.sup.an,
R.sup.ao, R.sup.ap is independently selected from: H, a straight
chain alkyl group having 1 to 22 carbon atoms, or a branched alkyl
group having 3 to 22 carbon atoms; R.sup.48 has the formula:
##STR00122## wherein each of R.sup.ag, R.sup.ar, R.sup.at, is
independently selected from: H, a straight chain alkyl group having
1 to 22 carbon atoms, a halogen atom, or a branched alkyl group
having 3 to 22 carbon atoms, wherein R.sup.as is selected from: H,
a straight chain alkyl group having 1 to 22 carbon atoms, a halogen
atom, an ester group, or a branched alkyl group having 3 to 22
carbon atoms, wherein R.sup.au is selected from: H, a straight
chain alkyl group having 1 to 22 carbon atoms, a halogen atom, a
cyano group, a nitro group, or a branched alkyl group having 1 to
22 carbon atoms.
39. A fluid according to claim 27 including a dye compound
according to Formula 4, wherein R.sup.50 and R.sup.51 are each H,
R.sup.53 and R.sup.54 together form: ##STR00123## wherein each of
R.sup.64, R.sup.65, R.sup.66, R.sup.67 is H, and R.sup.52 has the
formula: ##STR00124## wherein R.sup.55 is the alkoxy group having
the formula --O--R.sup.x, wherein R.sup.x is an alkyl group
selected from: an alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 22 carbon atoms, a straight
chain alkyl group having 1 to 8 carbon atoms, a straight chain
alkyl group having 8 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, a branched alkyl group having 3 to 8 carbon
atoms, a branched alkyl group having 8 carbon atoms, or a branched
alkyl group having the formula: ##STR00125## R.sup.56, R.sup.58 and
R.sup.59 are H, and R.sup.57 is the amino group having the formula
--N(R.sup.y)(R.sup.z), wherein each of R.sup.y and R.sup.z
independently is selected from: H, or an alkyl group selected from:
an alkyl group having 1 to 22 carbon atoms, a straight chain alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 8 carbon atoms, a straight chain alkyl group having 8
carbon atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00126##
40. A fluid according to claim 27 including a dye compound
according to Formula 4, selected from: a formula wherein R.sup.50,
R.sup.51, R.sup.53 are each H; R.sup.54 is the amide group having
the formula --NH--C(.dbd.O)R.sup.aj wherein R.sup.aj is selected
from H, or an alkyl group selected from: an alkyl group having 1 to
22 carbon atoms, a straight chain alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 8 carbon atoms, a
straight chain alkyl group having 8 carbon atoms, a branched alkyl
group having 3 to 22 carbon atoms, a branched alkyl group having 3
to 8 carbon atoms, a branched alkyl group having 8 carbon atoms, a
methyl group, or a branched alkyl group having the formula:
##STR00127## R.sup.55 is an alkyl group selected from: an alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 8 carbon atoms, a straight chain alkyl group having 8 carbon
atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a methyl group; R.sup.56, R.sup.58
and R.sup.59 are H; R.sup.57 is an alkyl group selected from: an
alkyl group having 1 to 22 carbon atoms, a straight chain alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 8 carbon atoms, a straight chain alkyl group having 8
carbon atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula: ##STR00128## or the formula: ##STR00129##
41. Electrowetting apparatus including a fluid including at least
one dye compound selected from: ##STR00130## wherein R.sup.5 is H;
R.sup.6 is an alkoxy group having the formula --O--R.sup.a, wherein
R.sup.a is an alkyl group; R.sup.7 is selected from: an amino group
having the formula --N(R.sup.b)(R.sup.c), wherein each of R.sup.b
and R.sup.c is an alkyl group, or --N.dbd.N--Het.sup.1 wherein
Het.sup.1 is a heterocyclic group; R.sup.8 is H; R.sup.9 is
selected from: an alkoxy group having the formula --O--R.sup.d,
wherein R.sup.d is an alkyl group; an amide group having the
formula --NH--C(.dbd.O)R.sup.e, wherein R.sup.e is an alkyl group;
a sulphonamide group having the formula
--NH--S(.dbd.O)(.dbd.O)--R.sup.f, wherein R.sup.f is an alkyl
group, or an amidophosphate group having the formula
--NH--P(.dbd.O)(--O--R.sup.g).sub.2, wherein R.sup.g is
independently an alkyl group, R.sup.10 has the formula B-A-, where
B has the formula: ##STR00131## where R.sup.11 is H; R.sup.12 is
selected from: H, a cyano group having the formula --CN, an alkoxy
group having the formula --O--R.sup.h, wherein R.sup.h is an alkyl
group, an alkyl group R.sup.i, or a halogen atom; R.sup.13 is
selected from: H, a cyano group having the formula --CN, an alkyl
group R.sup.j, or a halogen atom; R.sup.14 is selected from: H, a
cyano group having the formula --CN, a nitro group having the
formula --NO.sub.2, or an alkoxy group having the formula
--O--R.sup.k, wherein R.sup.k is an alkyl group; R.sup.15 is
selected from: a cyano group having the formula --CN, a nitro group
having the formula --NO.sub.2, an ester group having the formula
--COO--R.sup.l, wherein R.sup.l is an alkyl group, an alkoxy group
having the formula --O--R.sup.m, wherein R.sup.m is an alkyl group,
an alkyl group R.sup.n, a halogen atom, or a sulphonyl group having
the formula --SOOOH; wherein A is selected from: a single bond, a
formula selected from the group consisting of: ##STR00132## wherein
R.sup.16 is H; R.sup.17 is selected from: H, or an alkoxy group
having the formula --O--R.sup.o, wherein R.sup.o is an alkyl group;
R.sup.18 is H; R.sup.19 is selected from: H, or an alkoxy group
having the formula --O--R.sup.p, wherein R.sup.p is an alkyl group;
##STR00133## wherein R.sup.30 is selected from: OH, or an amino
group having the formula --N(R.sup.q)(R.sup.r), wherein R.sup.q is
H and R.sup.r is an alkyl group; an alkoxy group having the formula
--O--R.sup.ae, wherein R.sup.ae is an alkyl group; or a thioalkyl
group having the formula --S--R.sup.af, wherein R.sup.af is an
alkyl group, R.sup.31 is selected from: H, or has the formula
--X--Y, wherein X is selected from: --S--, a single bond, or --O--;
Y is selected from: --R.sup.s, or --R.sup.A, wherein R.sup.s is an
alkyl group and R.sup.A is an aryl group; R.sup.32 is H; R.sup.33
is selected from: an amino group having the formula
--N(R.sup.t)(R.sup.u), wherein R.sup.t is H and R.sup.u is an alkyl
group, an alkoxy group having the formula --O--R.sup.af, wherein
R.sup.af is an alkyl group, or a thioalkyl group having the formula
--S--R.sup.ag, wherein R.sup.ag is an alkyl group; R.sup.34 and
R.sup.35 are selected from the following: R.sup.34 and R.sup.35 are
each H, or together R.sup.34 and R.sup.35 form: ##STR00134##
wherein R.sup.36, R.sup.38 and R.sup.39 are each independently
selected from: H, or an alkyl group; R.sup.37 is selected from: H,
an alkyl group, or an ester group having the formula
--COO--R.sup.ah, wherein R.sup.ah is an alkyl group; ##STR00135##
wherein each of R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45, R.sup.46 is independently selected from: H, an alkoxy
group, an alkyl group, or an amino group having the formula
--N(R.sup.v)(R.sup.w), wherein R.sup.v is H and R.sup.w is one of:
H, or an alkyl group; wherein R.sup.47 is an arylene group and
R.sup.48 is an aryl group; ##STR00136## where R.sup.50 and R.sup.51
are independently selected from: H, or an amide group having the
formula --NH--C(.dbd.O)R.sup.aj wherein R.sup.aj is selected from
H, or an alkyl group, or together R.sup.50 and R.sup.51 form:
##STR00137## wherein each of R.sup.60, R.sup.61, R.sup.62, R.sup.63
is independently H or an alkyl group; R.sup.53 and R.sup.54 are
selected from the following: R.sup.53 and R.sup.54 are each H, or
together R.sup.53 and R.sup.54 form: ##STR00138## wherein each of
R.sup.64, R.sup.65, R.sup.66, R.sup.67 is independently H or an
alkyl group; R.sup.52 has the formula: ##STR00139## wherein
R.sup.55 is selected from: an alkoxy group having the formula
--O--R.sup.x, wherein R.sup.x is an alkyl group, an alkyl group, or
a halogen atom; R.sup.57 is an amino group having the formula
--N(R.sup.y)(R.sup.z), wherein each of R.sup.y and R.sup.z
independently is selected from: H, or an alkyl group; each of
R.sup.56, R.sup.58 and R.sup.59 is independently selected from: H,
or an alkyl group
42. A dye compound selected from: ##STR00140## wherein R.sup.5 is
H; R.sup.6 is an alkoxy group having the formula --O--R.sup.a,
wherein R.sup.a is an alkyl group; R.sub.7 is selected from: an
amino group having the formula --N(R.sup.b)(R.sup.c), wherein each
of R.sup.b and R.sup.c is an alkyl group, or --N.dbd.N--Het.sup.1
where Het.sup.1 is a heterocyclic group; R.sup.8 is H; R.sup.9 is
selected from: an alkoxy group having the formula --O--R.sup.d,
wherein R.sup.d is an alkyl group; an amide group having the
formula --NHC(.dbd.O)R.sup.e, wherein R.sup.e is an alkyl group; a
sulphonamide group having the formula
--NH--S(.dbd.O)(.dbd.O)--R.sup.f, wherein R.sup.f is an alkyl
group, or an amidophosphate group having the formula
--NH--P(.dbd.O)(--O--R.sup.g).sub.2, wherein R.sup.g is
independently an alkyl group, R.sup.m has the formula B-A-, wherein
B has the formula: ##STR00141## wherein R.sup.11 is H; R.sup.12 is
selected from: H, a cyano group having the formula --CN, an alkoxy
group having the formula --O--R.sup.h, wherein R.sup.h is an alkyl
group, an alkyl group or a halogen atom; R.sup.13 is selected from:
H, a cyano group having the formula --CN, an alkyl group R.sup.j,
or a halogen atom; R.sup.14 is selected from: H, a cyano group
having the formula --CN, a nitro group having the formula
--NO.sub.2, or an alkoxy group having the formula --O--R.sup.k,
wherein R.sup.k is an alkyl group; R.sup.15 is selected from: a
cyano group having the formula --CN, a nitro group having the
formula --NO.sub.2, an ester group having the formula
--COO--R.sup.l, wherein R.sup.l is an alkyl group, an alkoxy group
having the formula --O--R.sup.m, wherein R.sup.m is an alkyl group,
an alkyl group R.sup.n, a halogen atom, or a sulphonyl group having
the formula --SOOOH; wherein A is selected from: a single bond, a
formula selected from the group consisting of: ##STR00142## wherein
R.sup.16 is H; R.sup.17 is selected from: H, or an alkoxy group
having the formula --O--R.sup.o, wherein R.sup.o is an alkyl group;
R.sup.18 is H; R.sup.19 is selected from: H, or an alkoxy group
having the formula --O--R.sup.p, wherein R.sup.p is an alkyl group;
##STR00143## wherein R.sup.30 is selected from: OH, or an amino
group having the formula --N(R.sup.q)(R.sup.r), wherein R.sup.q is
H and R.sup.r is an alkyl group; an alkoxy group having the formula
--O--R.sup.ae, wherein R.sup.ae is an alkyl group; or a thioalkyl
group having the formula --S--R.sup.af, wherein R.sup.af is an
alkyl group, R.sup.31 is selected from: H, or has the formula
--X--Y, wherein X is selected from: --S--, a single bond, or --O--;
Y is selected from: --R.sup.s, or --R.sup.A, wherein R.sup.s is an
alkyl group and R.sup.A is an aryl group; R.sup.32 is H; R.sup.33
is selected from: an amino group having the formula
--N(R.sup.t)(R.sup.u), wherein R.sup.t is H and R.sup.o is an alkyl
group, an alkoxy group having the formula --O--R.sup.af, wherein
R.sup.af is an alkyl group, or a thioalkyl group having the formula
--S--R.sup.ag, wherein R.sup.ag is an alkyl group; R.sup.34 and
R.sup.35 are selected from the following: R.sup.34 and R.sup.35 are
each H, or together R.sup.34 and R.sup.35 form: ##STR00144##
wherein R.sup.36, R.sup.38 and R.sup.39 are each independently
selected from: H, or an alkyl group; R.sup.37 is selected from: H,
an alkyl group, or an ester group having the formula
--COO--R.sup.ah, wherein R.sup.ah is an alkyl group; ##STR00145##
wherein each of R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45, R.sup.46 is independently selected from: H, an alkoxy
group, an alkyl group, or an amino group having the formula
--N(R.sup.v)(R.sup.w), wherein R.sup.v is H and R.sup.w is one of:
H, or an alkyl group; wherein R.sup.47 is an arylene group and
R.sup.48 is an aryl group; ##STR00146## wherein R.sup.50 and
R.sup.51 are independently selected from: H, or an amide group
having the formula --NHC(.dbd.O)R.sup.aj wherein R.sup.aj
independently is selected from H, or an alkyl group, or together
R.sup.50 and R.sup.51 form: ##STR00147## wherein each of R.sup.60,
R.sup.61, R.sup.62, R.sup.63 is independently H or an alkyl group;
R.sup.53 and R.sup.54 are selected from the following: R.sup.53 and
R.sup.54 are each H, or together R.sup.53 and R.sup.54 form:
##STR00148## wherein each of R.sup.64, R.sup.65, R.sup.66, R.sup.67
is independently H or an alkyl group; R.sup.52 has the formula:
##STR00149## wherein R.sup.55 is selected from: an alkoxy group
having the formula --O--R.sup.x, wherein R.sup.x is an alkyl group,
an alkyl group, or a halogen atom; R.sup.57 is an amino group
having the formula --N(R.sup.y)(R.sup.z), wherein each of R.sup.y
and R.sup.z independently is selected from: H, or an alkyl group;
each of R.sup.56, R.sup.58 and R.sup.59 is independently selected
from: H, or an alkyl group.
Description
BACKGROUND
[0001] Display devices, for example electrowetting display devices,
are known. Display elements of such a display device may each
include a first fluid and a second fluid immiscible with the first
fluid. A display effect providable by each display element is
controllable in dependence on a configuration of the first and
second fluids, which configuration is changeable using an applied
voltage.
[0002] During manufacture of known display devices, it is necessary
to provide a suitable and accurately dispensed volume of the first
fluid in the display elements.
[0003] It is desirable to improve a method of providing the first
fluid during manufacturing of an electrowetting apparatus.
BRIEF DESCRIPTION OF DRAWINGS
[0004] FIG. 1 shows schematically an example electrowetting display
element; and
[0005] FIG. 2 shows a plan view of the example display element.
DETAILED DESCRIPTION
[0006] Details of substituent groups and atoms which will be
referred to herein are first described. These meanings apply unless
explicitly stated to the contrary.
[0007] An alkyl group as referred to herein is a straight chain,
branched or cyclic alkyl group. In examples, there are one or more
carbon atoms in the alkyl group, for example in some examples
having up to 30 carbon atoms, i.e. with 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26,
27, 28, 29, or 30 carbon atoms, for example having 1 to 4, 5 to 8,
9 to 12, 13 to 16, 17 to 20, 21 to 24, 25 to 30 carbon atoms, or
any other sub-range within the range 1 to 30. In examples, a
straight chain alkyl group may have 1 to 30 carbon atoms; in other
examples, a branched chain alkyl group may have 3 to 30 carbon
atoms; and in further examples a cyclic alkyl group may have 5 to
30 carbon atoms. In other examples the alkyl group has up to 22
carbon atoms, i.e. with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,
14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms, for example
having 1 to 4, 5 to 8, 9 to 12, 13 to 16, 17 to 20, 21 to 22 carbon
atoms, or any other sub-range within the range 1 to 22. In
examples, a straight chain alkyl group may have 1 to 22 carbon
atoms; in other examples, a branched chain alkyl group may have 3
to 22 carbon atoms; and in further examples a cyclic alkyl group
may have 5 to 22 carbon atoms. In a branched alkyl group described
herein, there may be one, two or three branched carbon atoms.
Further examples of alkyl groups are described later.
[0008] A haloalkyl group referred to herein is an alkyl group in
accordance with the description of an alkyl group given in the
paragraph above but with one, two or three of the hydrogen atoms
replaced by a halogen atom, for example any of fluorine (F),
chlorine (Cl), bromine (Br) and iodine (I); in some examples a
halogen atom is bromine (Br). It is noted that a halogen atom
referred to herein which is not part of a haloalkyl group is one of
the halogen atoms listed here.
[0009] Any aryl group referred to herein is a monovalent aromatic
hydrocarbon group having five, six or seven carbon atoms, for
example any aromatic hydrocarbon having C.sub.5 to C.sub.7 carbon
atoms, i.e. 5, 6 or 7 carbon atoms. Further, any such aryl group
may be substituted on at least one aromatic carbon by for example,
as defined herein, an alkyl group as defined herein, or another
substituent as will be explained with reference to examples further
below. The aryl group may have one, two, three, four or five
substituent groups. Such an aryl group may for example be a phenyl
group.
[0010] Any arylene group referred to herein is a divalent aromatic
hydrocarbon group, with the divalent bonding sites being configured
according to any of -ortho, -meta or -para sites for a six membered
ring, at any of the 1 to 5 positions for a five membered ring, at
any of the 1 to 6 positions for a six membered ring and at any of
the 1 to 7 positions for a seven membered ring. Further, any such
arylene group may for example be a single ring structure formed of
five, six or seven carbon atoms which ring may be substituted on at
least one aromatic carbon by an alkyl group as defined herein, or
another substituent for example as will be explained with reference
to examples further below. The arylene group may have one, two,
three or four substituent groups.
[0011] Any alkoxy group referred to herein is an alkyl group in
accordance with an alkyl group described herein, bonded to an
oxygen, for example with the formula --O-alkyl.
[0012] A hydroxyl group referred to herein is the group --OH.
[0013] A heterocyclic group referred to herein includes saturated
and unsaturated hydrocarbon groups with at least one heteroatom,
for example nitrogen (N) or oxygen (O). For example, such an
unsaturated group may be an aromatic hydrocarbon group with at
least one heteroatom, for example nitrogen (N) or oxygen (O)
conjugated in the aromatic system. The aromatic hydrocarbon group
may form a five or six membered ring, including one, two or three
heteroatoms, for example, and a number of carbon atoms to complete
the ring, for example in the range C.sub.2 to C.sub.5, i.e. 2, 3, 4
or 5 carbon atoms. In other examples, such a saturated heterocyclic
group may be a cyclic alkyl group referred to herein, with at least
one of the carbon atoms of the cyclic alkyl group substituted with
a heteroatom such as nitrogen (N) or oxygen (O). Such a saturated
heterocyclic group may be a five or six membered ring, including
one, two or three heteroatoms, for example, and a number of carbon
atoms to complete the ring, for example in the range C.sub.2 to
C.sub.5, i.e. 2, 3, 4 or 5 carbon atoms. Examples of such
heterocyclic groups include a pyrrole group, a pyridine group, a
furan group, a pyran group, a pyrrolidine group, a piperidine
group, a tetrahydroofuran group, or an oxane group. The
heterocyclic group may have one or more substituent groups bonded
to the heterocycle group, for example at any of the 2, 3 and where
appropriate 4 positions. Such substituent groups may be H or an
alkyl group.
[0014] An amino group referred to herein includes any primary,
secondary or tertiary amino, i.e. --NH.sub.2 substituted
respectively with zero, one or two alkyl or aryl groups as defined
herein.
[0015] A nitro group referred to herein is the group --NO.sub.2,
i.e. including a nitrogen atom bonded to two oxygen atoms.
[0016] A cyano group referred to herein is the group --CN, i.e. a
carbon atom bonded with a triple bond to a nitrogen. Such a group
might alternatively be referred to as a nitrile group; i.e. a
carbon with a triply bonded nitrogen substituent.
[0017] An amide group referred to herein is a group with a nitrogen
bonded to a carboxy group, with the nitrogen being further
substituted by two of a hydrogen atom, an alkyl group or an aryl
group defined herein; i.e. for example having the formula
--C(.dbd.O)N(AG).sub.2 where AG indicates an alkyl or aryl group
defined herein.
[0018] A sulphonyl group referred to herein is a group with a
sulphur atom bonded to two oxygen atoms via two double bonds. The
sulphur atom is further bonded by a single bond to a hydrocarbon
group such as an alkyl or an aryl group labelled AG and defined
herein; i.e. --SO.sub.2(AG).
[0019] A sulphonamide group referred to herein is a group with a
sulphur atom bonded to two oxygen atoms via two double bonds and
further bonded to a nitrogen atom which is bonded in turn either to
two hydrogen atoms, to one alkyl or aryl group defined herein and
to a hydrogen, or to two alkyl or aryl groups defined herein.
Depending on the number of nitrogen substitutions, a sulphonamide
group may have the formula: --S(.dbd.O)(.dbd.O)N(H).sub.2,
--S(.dbd.O)(.dbd.O)N(H)(AG) or --S(.dbd.O)(.dbd.O)N(AG).sub.2 where
AG is an alkyl or aryl group defined herein.
[0020] An amidophosphate group referred to herein is a group with a
nitrogen bonded to a hydrogen atom and to a phosphorous atom. Such
a group may also be referred to as a phosphoramidate. In such a
group, the phosphorous atom is in turn bonded to one oxygen atom
with a double bond and to the oxygen atom of each of two alkoxy
groups defined herein. Such an amidophosphate group may therefore
have the formula: --NH--P(.dbd.O)(--O-AG).sub.2 where AG is an
alkyl or aryl group defined herein.
[0021] An ester group referred to herein is a group with a carbon
atom doubly bonded to an oxygen atom and further singly bonded to
an oxygen atom which in turn is bonded to an alkyl or an aryl group
defined herein. Such an ester group may therefore have the formula
--C(.dbd.O)--O-AG, i.e. COOAG, where AG is an alkyl or aryl group
defined herein.
[0022] A thioalkyl group referred to herein includes any isomer of
a thioalkyl group, i.e. an alkyl group, bonded to a sulphur, having
the formula --S-alkyl where--alkyl is an alkyl group defined
herein.
[0023] Examples will now be described.
[0024] FIG. 1 shows a diagrammatic cross-section of part of an
example of an electrowetting display device 1, including a
plurality of picture elements or display elements 2, one of which
is shown in the Figure and which may also be referred to as an
electrowetting cell or an electrowetting pixel. The lateral extent
of the display element is indicated in the Figure by two dashed
lines 3, 4. The display elements comprise a first support plate 5
and a second support plate 6. The support plates may be separate
parts of each display element, but the support plates may be shared
in common by the plurality of display elements. The support plates
may include a glass or polymer substrate 6, 7 and may be rigid or
flexible.
[0025] The display device has a viewing side 8 on which an image or
display formed by the display device can be viewed and a rear side
9. In the Figure a surface of the first support plate 5, which
surface is in this example a surface of the substrate 7, defines
the rear side 9; a surface of the second support plate 6, which
surface is in this example a surface of the substrate 6, defines
the viewing side; alternatively, in other examples, a surface of
the first support plate may define the viewing side. The display
device may be of the reflective, transmissive or transflective
type. The display device may be an active matrix driven display
device. The plurality of display elements may be monochrome. For a
colour display device the display elements may be divided in
groups, each group having a different colour; alternatively, an
individual display element may be able to show different
colours.
[0026] A space 10 of each display element between the support
plates is filled with two fluids: a first fluid 11 and a second
fluid 12 at least one of which may be a liquid. The second fluid is
immiscible with the first fluid. Therefore, the first fluid and the
second fluid do not substantially mix with each other and in some
examples do not mix with each other to any degree. The
immiscibility of the first and second fluids is due to the
properties of the first and second fluids, for example their
chemical compositions; the first and second fluids tend to remain
separated from each other, therefore tending not to mix together to
form a homogeneous mixture of the first and second fluids. Due to
this immiscibility, the first and second fluids meet each other at
an interface labelled 55 in FIG. 1 for when no voltage is applied
and labelled 57 for when a voltage is applied, which interface
defines a boundary between the volume of the first fluid and the
volume of the second fluid; this interface or boundary may be
referred to as a meniscus. With the first and second fluids
substantially not mixing with each other, it is envisaged in some
examples that there may be some degree of mixing of the first and
second fluids, but that this is considered negligible in that the
majority of the volume of first fluid is not mixed with the
majority of the volume of the second fluid.
[0027] The second fluid is electrically conductive or polar and may
be water, or a salt solution such as a solution of potassium
chloride in water. The second fluid may be transparent; it may
instead be coloured, white, absorbing or reflecting. Details of the
chemical composition of the first fluid, which is electrically
non-conductive, are explained further below.
[0028] The first fluid may absorb at least a part of the optical
spectrum. The first fluid may be transmissive for a part of the
optical spectrum, forming a colour filter. For this purpose the
first fluid may be coloured by addition of pigment particles or a
dye. Alternatively, the first fluid may be black, i.e. absorb
substantially all parts of the optical spectrum, or reflecting. A
reflective first fluid may reflect the entire visible spectrum,
making the layer appear white, or part of it, making it have a
colour.
[0029] The support plate 5 includes an insulating layer 13. The
insulating layer may be transparent or reflective. The insulating
layer 13 may extend between walls of a display element. To avoid
short circuits between the second fluid 12 and electrodes arranged
under the insulating layer, layers of the insulating layer may
extend uninterrupted over a plurality of display elements 2, as
shown in the Figure. The insulating layer has a surface 14 facing
the space 10 of the display element 2. In this example the surface
14 is hydrophobic. The thickness of the insulating layer may be
less than 2 micrometers and may be less than 1 micrometer.
[0030] The insulating layer may be a hydrophobic layer;
alternatively, it may include a hydrophobic layer 15 and a barrier
layer 16 with predetermined dielectric properties, the hydrophobic
layer 15 facing the space 10, as shown in the Figure. The
hydrophobic layer is schematically illustrated in FIG. 1 and may be
formed of Teflon.RTM. AF1600. The barrier layer 16 may have a
thickness, taken in a direction perpendicular the plane of the
substrate, between 50 nanometers and 500 nanometers and may be made
of an inorganic material like silicon oxide or silicon nitride or a
stack of these (for example, silicon oxide-silicon nitride-silicon
oxide) or an organic material like polyimide or parylene.
[0031] The hydrophobic character of the surface 14 causes the first
fluid 11 to adhere preferentially to the insulating layer 13, since
the first fluid has a higher wettability with respect to the
surface of the insulating layer 13 than the second fluid 12.
Wettability relates to the relative affinity of a fluid for the
surface of a solid. Wettability may be measured by the contact
angle between the fluid and the surface of the solid. The contact
angle is determined by the difference in surface tension between
the fluid and the solid at the fluid-solid boundary. For example, a
high difference in surface tension can indicate hydrophobic
properties.
[0032] Each display element 2 includes a first electrode 17 as part
of the support plate 5. In examples shown there is one such
electrode 17 per element. The electrode 17 is electrically
insulated from the first and second fluids by the insulating layer
13; electrodes of neighboring display elements are separated by a
non-conducting layer. In some examples, further layers may be
arranged between the insulating layer 13 and the electrode 17. The
electrode 17 can be of any desired shape or form. The electrode 17
of a display element is supplied with voltage signals by a signal
line 18, schematically indicated in the Figure.
[0033] The support plate 6 includes a second electrode 19, which
may extend between walls of a display element or extend
uninterruptedly over a plurality of display elements 2, as shown in
the Figure. The electrode 19 is in electrical contact with the
conductive second fluid 12 and is common to all display elements.
The electrode may be made of for example the transparent conductive
material indium tin oxide (ITO). A second signal line 20 is
connected to the electrode 19. Alternatively, the electrode may be
arranged at a border of the support plates, where it is in
electrical contact with the second fluid. This electrode may be
common to all elements, when they are fluidly interconnected by and
share the second fluid, uninterrupted by walls. The display element
2 can be controlled by a voltage V applied between the signal lines
18 and 20. The signal line 18 can be coupled to a matrix of control
lines on the substrate 7. The signal line 20 is coupled to a
display driving system.
[0034] The first fluid 11 in this example is confined to one
display element by walls 21 that follow the cross-section of the
display element. The cross-section of a display element may have
any shape; when the display elements are arranged in a matrix form,
the cross-section is usually square or rectangular. Although the
walls are shown as structures protruding from the insulating layer
13, they may instead be a surface layer of the support plate that
repels the first fluid, such as a hydrophilic or less hydrophobic
layer. The walls may extend from the first to the second support
plate but may instead extend partly from the first support plate to
the second support plate as shown in FIG. 1. The extent of the
display element, indicated by the dashed lines 3 and 4, is defined
by the center of the walls 21. The area of the surface 14 between
the walls of a display element, indicated by the dashed lines 22
and 23, is called the display area 24, over which a display effect
occurs. The display effect depends on an extent that the first and
second fluids adjoin the surface defined by the display area, in
dependence on the magnitude of the applied voltage V described
above. The magnitude of the applied voltage V therefore determines
the configuration of the first and second fluids within the
electrowetting element. In other words, the display effect depends
on the configuration of the first and second fluid in the display
element, which configuration depends on the magnitude of the
voltage applied to the electrodes of the display element. The
display effect gives rise to a display state of the display element
for an observer looking at the display device. When switching the
electrowetting element from one fluid configuration to a different
fluid configuration the extent of second fluid adjoining the
display area surface may increase or decrease, with the extent of
first fluid adjoining the display area surface decreasing or
increasing, respectively.
[0035] FIG. 2 shows a matrix of rectangular picture elements in a
plan view of the hydrophobic surface 14 of the first support plate.
The extent of the central picture element in FIG. 2, corresponding
to the dashed lines 3 and 4 in FIG. 1, is indicated by the dashed
line 26. Line 27 indicates the inner border of a wall; the line is
also the edge of the display area 23.
[0036] When a zero or substantially zero voltage is applied between
the electrodes 17 and 19, i.e. when the electrowetting element is
in an off state, the first fluid 11 forms a layer between the walls
21, as shown in the FIG. 1. Application of a voltage will contract
the first fluid, for example against a wall as shown by the dashed
shape 25 in FIG. 1 or FIG. 2. The controllable shape of the first
fluid, in dependence on the magnitude of applied voltage, is used
to operate the picture element as a light valve, providing a
display effect over the display area 23. For example, switching the
fluids to increase adjoinment of the second fluid with the display
area may increase the brightness of the display effect provided by
the element.
[0037] This display effect determines the display state an observer
will see when looking towards the viewing side of the display
device. The display state can be from black to white with any
intermediate grey state; in a colour display device, the display
state may also include colour.
[0038] In known electrowetting display devices, the first fluid
referred to above may comprise for example an alkane or silicone
oil. It has now been observed that whilst such compounds exhibit
many desirable properties for their use in an electrowetting
display element, a lower vapour pressure would be desirable, for
example to aid manufacture of the display elements.
[0039] Given the many numerous chemical compounds available, it is
a complex and non-routine task to identify new compounds which
offer suitable properties for the first fluid of an electrowetting
display element. For example, properties of suitable compounds may
include any of the following, though further properties are
envisaged: suitable switching performance when a voltage is applied
to change a configuration of the first and second fluids; a
suitable viscosity, for example to aid the switching performance;
suitable solvent properties, for example so the compound may
function as a carrier fluid for a dye to be dissolved therein, so
for example the first fluid provides reliable display effects in a
variety of lighting conditions and temperature ranges; suitable
safety properties, for example for manufacture and for the
consumer; cost-effective; suitable immiscibility with the second
fluid; and suitable optical transparency. Such properties apply to
carrier fluid compounds and also where appropriate to dye
compounds.
[0040] One property of such a first fluid compound, for example
which functions as a carrier fluid, is a suitable vapour pressure.
If the vapour pressure is too high, manufacturing a display element
may be more complicated, given the volatility of the first fluid
compound and its tendency to evaporate. This can for example lead
to a reduced and/or inaccurately dispensed volume of the first
fluid in the manufactured display elements and may also require
more controlled and complex manufacturing techniques for handling
the first fluid both safely and effectively to minimise
evaporation.
[0041] New classes of chemical compounds for the first fluid in an
electrowetting apparatus have now been identified. These compounds
have a reduced vapour pressure compared with known first fluid
compounds. Therefore a method of manufacturing an electrowetting
apparatus may be simplified; further a volume of first fluid may be
more accurately provided in a display element. Furthermore, it has
been found that these new classes of compounds exhibit many other
suitable properties required for them to perform suitably in an
electrowetting display element, for example optical transparency
and for example a suitable non-polar property for their function in
an electrowetting display element. Indeed, these newly identified
compounds offer properties which are at least comparable, but in
some examples better overall, than known first fluid compounds.
[0042] For example, a viscosity of these newly identified compounds
is sufficiently low to offer suitable performance in an
electrowetting display element. It would be expected that to
decrease a vapour pressure, a less volatile and therefore more
viscous fluid would be required. However, the newly identified
compound classes for electrowetting offer both a comparable
viscosity with known first fluid compounds and moreover offer a
reduced vapour pressure compared with such known compounds. Thus,
the newly identified compounds for electrowetting offer an improved
balance of vapour pressure and viscosity properties compared with
known compounds.
[0043] In examples, the newly identified classes of compounds for
electrowetting have a vapour pressure with a maximum value of 5
millimetres mercury (i.e. 5 mm Hg) when measured at a temperature
of 20.degree. Celsius. A dynamic viscosity of any such newly
identified compound may be at most, i.e. less than or equal to, 37
centiPoise (cP) when measured at a temperature of 20.degree.
Celsius and in some examples greater than or equal to 0.5 cP; in
some examples the dynamic viscosity of at least one of the
compounds is in the range of: 0.5 to 37 cP, 0.5 to 35 cP, 0.5 to 30
cP, 0.5 to 25 cP, 0.5 to 20 cP, 0.5 to 15 cP, 0.5 to 10 cP, 0.5 to
9 cP, 0.5 to 8 cP, 0.5 to 7 cP. In other examples the dynamic
viscosity in one of the following ranges may offer a particularly
suitable viscosity for electrowetting performance: 0.5 to 6 cP, 0.5
to 5.5 cP, 0.5 to 5.0 cP, 0.5 to 4.5 cP, 0.5 to 4.0 cP, 0.5 to 3.5
cP, or 0.5 to 3.0 cP, when measured at a temperature of 20.degree.
Celsius. The dynamic viscosity values given herein are based on
measurements taken with a Brookfield DVII+ pro viscosmeter for low
viscosities with a CPE40 spindle (0.5.degree. cone angle). Although
specific values of dynamic viscosity and vapour pressure are given
herein, it is to be appreciated that some variation from those
values, within for example an accepted tolerance for error due to
measuring techniques, is envisaged. Therefore, the term "about" may
be used in association with any of the specified values.
[0044] In examples, the newly identified classes of compounds for
the first fluid, for example which may act as a solvent, i.e. a
carrier fluid, for at least one dye dissolved in the solvent,
include any of:
a silane compound having the following general formula:
##STR00003##
where Si is silicon; and and a germane compound having the
following general formula:
##STR00004##
where Ge is germanium.
[0045] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each an alkyl
group Therefore, the compound including silicon may be referred to
as a tetraalkylsilane and the compound including germanium may be
referred to as a tetraalkylgermane.
[0046] Any alkyl group referred to herein for any of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 includes any isomer of a straight
chain or branched alkyl group. In examples, there are one or more
carbon atoms in the alkyl group; for a branched alkyl group the
minimum number of carbon atoms is 3, but may include a greater
number of carbon atoms in accordance with the specific total number
of carbon atom values listed below. For example, a total number of
carbon atoms contained by any one of the alkyl groups R.sup.1,
R.sup.2, R.sup.3, R.sup.4 may be at most, i.e. less than or equal
to, 30; in other words this total number may be 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29 or 30 carbon atoms and may for example be in
one of the ranges of 1 to 4 carbon atoms, 5 to 8 carbon atoms, 9 to
12 carbon atoms, 13 to 16 carbon atoms, 17 to 20 carbon atoms, 21
to 24 carbon atoms, 25 to 28 carbon atoms, and 27 to 30 carbon
atoms. Where any of the alkyl groups R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 is a branched alkyl group, a longest chain of carbon atoms
in any one of the alkyl groups R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 is at most, i.e. less than or equal to, 24 carbon atoms
long. Therefore, such a longest chain may be 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 carbon
atoms long and may for example have 3 to 6 carbon atoms, 7 to 10
carbon atoms, 11 to 14 carbon atoms, 15 to 18 carbon atoms, 19 to
22 carbon atoms or 21 to 24 carbon atoms.
[0047] In examples, a total number of carbon atoms contained by all
of the alkyl groups R.sup.1, R.sup.2, R.sup.3 and R.sup.4 when
taken together, i.e. the total number is the sum of the number of
carbon atoms of each of the alkyl groups R.sup.1, R.sup.2, R.sup.3
and R.sup.4, is at most, i.e. less than or equal to, 33 carbon
atoms. Therefore, depending on the configuration of the alkyl
groups this total number may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,
12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,
29, 30, 31, 32 or 33 carbon atoms, or may be in one of the ranges 1
to 4 carbon atoms, 5 to 8 carbon atoms, 9 to 12 carbon atoms, 13 to
16 carbon atoms, 17 to 20 carbon atoms, 21 to 24 carbon atoms, 25
to 28 carbon atoms, and 29 to 33 carbon atoms. This total may be
considered as the total number of carbon atoms in one molecule of
the solvent compound.
[0048] In examples, the alkyl group of each of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 is a saturated alkyl group. In other words,
each carbon-carbon bond in the alkyl group is a single bond, rather
than a double or triple bond for example.
[0049] By controlling the configuration of the alkyl groups
R.sup.1, R.sup.2, R.sup.3 and R.sup.4, for example in accordance
with numbers of carbon atoms described above, the properties of a
first fluid solvent compound may be tuned to provide an appropriate
viscosity for example in combination for example with a desirable
vapour pressure. Indeed, upper limits for the number of carbon
atoms described above, for example the upper limit of 24 carbon
atoms for the longest chain of carbon atoms in a branched alkyl
group, are selected to provide suitable viscosity properties. A
higher number of carbons than the specified upper limits may lead
to viscosity properties for example which are not suitable for use
in an electrowetting display element. Similarly, where any of the
alkyl groups R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are branched
alkyl groups, the extent of branching is selected to provide
suitable molecular properties, for example the viscosity. Each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in examples may have the same
branched alkyl group configuration or different ones of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 may have different branching
configurations compared with other ones of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4. Such branching may include secondary, tertiary
and quaternary branching, where a carbon atom is bonded to two,
three or four carbon atoms, respectively.
[0050] In some examples, the alkyl group of each of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 is a straight chain, i.e. unbranched,
alkyl group having the general formula --(CH.sub.2).sub.nCH.sub.3
where n is independently, for each of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4, in the range of 0 to 7. Therefore, the number of carbon
atoms in a straight chain alkyl group of any of R', R.sup.2,
R.sup.3 and R.sup.4 may be 1, 2, 3, 4, 5, 6, 7 or 8 and may be in
one of the ranges to 1 to 3 carbon atoms, 4 to 6 carbon atoms and 7
to 8 carbon atoms. The upper limit of n=7 carbon atoms (and
therefore a total number of carbon atoms in one alkyl group of 8)
applies where for example the number of carbon atoms contained by
each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is the same; thus, to
keep to within the upper limit of 33 carbon atoms described above
for the total number of carbon atoms of R1, R2, R3 and R4 when
taken together, the maximum number of carbon atoms per alkyl group
is 8 (i.e. 32 divided by 4), and the compound may therefore have
the formula Si--((CH.sub.2).sub.7CH.sub.3).sub.4 or
Ge--((CH.sub.2).sub.7CH.sub.3).sub.4.
[0051] Examples of such a compound of the first fluid will be now
be described, where each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4
contains the same number of carbon atoms. In examples, each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently a straight
chain alkyl group; in other examples each of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 is independently a branched alkyl group.
Example 1
[0052] In this example the compound has the following formula:
##STR00005##
where n=1 for each of R.sup.1, R.sup.2, R3 and R4 and the compound
may be referred to as tetraethylsilane (TES). The compound has a
vapour pressure of 4.4 mmHg when measured at 20.degree. Celsius and
a dynamic viscosity of 0.68 cP when measured at 20.degree. Celsius.
The compound may be obtained from Gelest, Inc., 11 East Steel Road,
Morrisville, Pa. 19067, USA, under product code SIT7115.0 or Tokyo
Chemical, Inc., 4-10-2 Nihonbashi-honcho, Chuo-ku, Tokyo 103-0023,
Japan, under product code T1552.
Example 2
[0053] In this example the compound has the following formula:
##STR00006##
where n=2 for each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 and the
compound may be referred to as tetrapropylsilane (TPS). The
compound has a dynamic viscosity of 1.34 cP when measured at
20.degree. Celsius. The compound may be synthesised for example as
follows:
[0054] To a mixture of 100.0 grams (g) magnesium (4.17 moles (mol))
and 200 millilitres (mL) tetrahydrofuran (THF) there was added 5 g
1-bromopropane. The mixture was cooled with a cold-water bath after
Grignard agent formation had started. 450 mL THF was added,
followed by the slow addition of 1-bromopropane (total amount 500
g, 4.065 mol) at temperatures between 20.degree. Celsius (.degree.
C.) and 75.degree. C. over a period of 21/2 hours. An additional
200 mL THF was added and the mixture was heated for 4 hours (h) at
60.degree. C., then it was cooled in ice. Silicon tetrachloride
(108.42 g, 0.638 mol) was added over a 21/2 h period at
15-38.degree. C. During this addition, another 250 mL THF was added
in order to maintain a well-stirrable suspension. The mixture was
heated for 1 h at 60.degree. C., stirred overnight, then heated for
8 h at 65.degree. C., and for 4 h at 75.degree. C. Water (50 mL)
and 6 normality (N) hydrochloric acid (100 mL) were added very
slowly to the suspension at ca. 60.degree. C. The mixture was
further diluted with 6N hydrochloric acid (500 mL) and stirred
mechanically for 3 h before the liquid was decanted and partially
concentrated on a rotary evaporator (i.e. a rotavap). The residue
was treated with 300 mL tertiary-butyl methyl ether (TBME), washed
with water and concentrated on the rotavap. After extraction with
pentane and heptane the combined organic layers were eluted over a
silica column with heptane. Rotary evaporation and Kugelrohr
distillation yielded 114.9 g of the product (0.573 mol, 90%
yield).
Example 3
[0055] In this example the compound has the following formula:
##STR00007##
where n=3 for each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 and the
compound may be referred to as tetrabutylsilane (TBS). The compound
has a dynamic viscosity of 3.69 cP when measured at 20.degree.
Celsius. The compound may be synthesised for example as
follows:
[0056] A mixture of chlorotributylsilane (25.0 g, 0.106 mol) and 75
mL heptane was cooled with an ice-bath. n-Butyllithium in hexanes
(70 mL 2.5 N, 0.175 mol) was added over a 20 minute period. The
cooling bath was removed and the mixture was stirred overnight,
then heated for 6 h at 60.degree. C. The mixture was cooled with
ice and 75 mL THF was added in portions, resulting in a temperature
rise to 35.degree. C. The mixture was stirred for 5 days, then 100
mL water was added. The layers were separated, the lower layer was
extracted with some heptane and the organic layers were dried over
sodium sulfate, then rotary evaporated. The residue was
chromatographed on 80 g silica, elution being performed with
heptane. Rotary evaporation of the eluate and Kugelrohr
distillation of the residue yielded 25.60 g of the product (99.8
mmol, 94% yield).
Example 4
[0057] In this example the compound has the following formula:
##STR00008##
where n=1 for each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4. The
compound may be referred to as tetraethylgermane (TEG). The
compound has a dynamic viscosity of 0.66 cP when measured at
20.degree. Celsius. The compound may be obtained from Gelest, Inc.
under product code no. GET7150 or Tokyo Chemical, Inc. under
product code no. T1157.
[0058] In further examples, the number of carbon atoms contained by
any one, for example one or more, of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 is different from a number of carbon atoms contained by a
different one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4. One example
is now described.
Example 5
[0059] In this example the compound has the following formula:
##STR00009##
[0060] where n=5 for each of R.sup.1 and R.sup.4, n=0 for R.sup.2
and n=4 for R.sup.3. The compound may be referred to as
trihexylmethylsilane (THMS). The compound has a dynamic viscosity
of 5.32 cP when measured at 20.degree. Celsius. The compound may be
obtained from Gelest, Inc. under product code no. SIM6559.0. The
silane and germane compounds described herein for the first fluid,
for examples those of examples 1 to 5, are found to function as a
suitable carrier fluid for use in an electrowetting display
element. Therefore, such a compound may act as a suitable solvent
for dissolving a dye compound used in an electrowetting display
element, to form an electrowetting ink for example, or may provide
a suitable medium for suspending pigment particles therein. Further
details of such dye compounds will be described in further detail
below. Suitable pigments may include for example carbon black, a
phthalocyanine pigment, an azo pigment or a diketopyrrolopyrrole
(DPP) pigment.
[0061] Examples of dye compounds will now be described. These dye
compounds are newly identified as being usable in an electrowetting
apparatus, for example in a first fluid described above, and have
at least one desirable property for functioning in an
electrowetting apparatus, for example the properties previously
described. Any such dye compound is at least partly dissolvable in
any of the examples of carrier fluid compounds described
previously, for example the silane and germane compounds described
above. Thus, a fluid including such a dye compound at least partly
dissolved in such a carrier fluid provides an effective first fluid
for electrowetting apparatus. In other examples any such dye
compound is at least partly dissolvable in other known carrier
fluids for the first fluid, for example silicone oil or an alkane
such as decane.
[0062] In examples, of a fluid for an electrowetting apparatus,
such as that described above, the fluid includes at least one azo
dye compound having the following formula:
##STR00010##
[0063] where R.sup.5 is H; R.sup.6 is an alkoxy group having the
formula --O--R.sup.a, where R.sup.a is an alkyl group; R.sup.7 is
selected from: an amino group having the formula
--N(R.sup.b)(R.sup.c), with each of R.sup.b and R.sup.c being an
alkyl group, or --N.dbd.N--Het.sup.1 where Het.sup.1 is a
heterocyclic group; R.sup.8 is H; R.sup.9 is selected from: an
alkoxy group having the formula --O--R.sup.d, where R.sup.d is an
alkyl group; an amide group having the formula
--NH--C(.dbd.O)R.sup.e, where R.sup.e is an alkyl group; a
sulphonamide group having the formula
--NH--S(.dbd.O)(.dbd.O)--R.sup.f, where R.sup.f is an alkyl group,
or an amidophosphate group having the formula
--NH--P(.dbd.O)(--O--R.sup.g).sub.2, where R.sup.g is independently
an alkyl group (each R.sup.g alkyl group of the amidophosphate
group may be the same or different), R.sup.10 has the formula
B-A-,
[0064] where B has the formula:
##STR00011##
[0065] where R.sup.11 is H; R.sup.12 is selected from: H, a cyano
group having the formula --CN, an alkoxy group having the formula
--O--R.sup.h, where R.sup.h is an alkyl group, an alkyl group
R.sup.i for example a methyl alkyl group, or a halogen atom;
R.sup.13 is selected from:
[0066] H, a cyano group having the formula --CN, an alkyl group
R.sup.j for example a methyl alkyl group, or a halogen atom;
R.sup.14 is selected from: H, a cyano group having the formula
--CN, a nitro group having the formula --NO.sub.2, or an alkoxy
group having the formula --O--R.sup.k, where R.sup.k is an alkyl
group; R.sup.15 is selected from: a cyano group having the formula
--CN, a nitro group having the formula --NO.sub.2, an ester group
having the formula --COO--R.sup.l, where R.sup.l is an alkyl group,
an alkoxy group having the formula --O--R.sup.m, where R.sup.m is
an alkyl group, an alkyl group R.sup.n, a halogen atom, or a
sulphonyl group having the formula --SOOOH;
[0067] where A is selected from: a single bond, the formula:
##STR00012##
or the formula:
##STR00013##
[0068] where R.sup.16 is H; R.sup.17 is selected from: H, or an
alkoxy group having the formula --O--R.sup.o, where R.sup.o is an
alkyl group; R.sup.18 is H; R.sup.19 is selected from: H, or an
alkoxy group having the formula --O--R.sup.p, where R.sup.p is an
alkyl group. Thus in some examples the dye compound may be a bisazo
dye compound.
[0069] In examples, the alkyl group of one or more of: R.sup.a,
R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g, R.sup.h,
R.sup.i, R.sup.j, R.sup.k, R.sup.l, R.sup.m, R.sup.n, R.sup.o,
R.sup.p is independently selected from: a straight chain alkyl
group having 1 to 22 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, or a cyclic alkyl group having 5 to 22 carbon
atoms.
[0070] In examples described above and below where an alkyl group
of a dye compound has a number of carbon atoms in the range of 1 to
22, it has been found that more than 22 carbon atoms can increase a
viscosity of a dye compound to the extent that it degrades its
performance within an electrowetting apparatus. Such alkyl groups
may in some examples instead be a haloalkyl group which includes a
bromide atom.
[0071] In some examples an alkyl group having the formula:
##STR00014##
is described herein; such an alkyl group offers suitable solubility
properties of the dye compound in a carrier fluid such as a silane
or germane carrier fluid described in examples herein.
[0072] Further, or in further examples where the dye compound is
according to Formula 1, R.sup.a is selected from:
[0073] a branched alkyl group having 3 to 22 carbon atoms,
[0074] a branched alkyl group having 3 to 8 carbon atoms,
[0075] a branched alkyl group having 8 carbon atoms, or
[0076] a branched alkyl group such that R.sup.6 has the
formula:
##STR00015##
[0077] Further, or in further examples where the dye compound is
according to Formula 1, R.sup.7 is the amino group having the
formula --N(R.sup.b)(R.sup.c), the alkyl group of R.sup.b and
R.sup.c are each independently selected from:
[0078] a straight chain alkyl group having 1 to 22 carbon
atoms,
[0079] a straight chain alkyl group having 1 to 8 carbon atoms,
[0080] a straight chain alkyl group having 8 carbon atoms,
[0081] a straight chain alkyl group having 6 carbon atoms,
[0082] a straight chain alkyl group having 1 to 5 carbon atoms,
[0083] a straight chain alkyl group having 5 carbon atoms,
[0084] a branched alkyl group having 3 to 22 carbon atoms,
[0085] a branched alkyl group having 3 to 8 carbon atoms,
[0086] a branched alkyl group having 8 carbon atoms,
[0087] a branched alkyl group such that the amino group of R.sup.7
has the formula:
##STR00016##
[0088] a straight chain alkyl group having 5 carbon atoms, or
[0089] a straight chain alkyl group having 4 carbon atoms.
[0090] In such examples, it is noted that a tertiary amino provides
suitable solubility in a carrier fluid, for example the silane or
germane examples described above. Primary and secondary aminos are
less soluble in such carrier fluids and are therefore less suitable
for use in an electrowetting apparatus.
[0091] Further, or in further examples where the dye compound is
according to Formula 1, R.sup.7 is --N.dbd.N--Het.sup.1 where
Het.sup.1 is a heterocyclic group selected from: a five membered
heterocyclic ring, a six membered heterocyclic ring, a five
membered heterocyclic aromatic ring containing 1 to 3 heteroatoms,
a six membered heterocyclic aromatic ring containing 1 to 3
heteroatoms, a five membered heterocyclic aromatic ring containing
1 heteroatom which is an N atom, a six membered heterocyclic
aromatic ring containing 1 heteroatom which is an N atom, a five
membered heterocyclic aromatic ring containing 1 heteroatom which
is an N atom, where the --N.dbd.N-- group is bonded to the
heterocyclic aromatic ring at the 2 position relative to the
heteroatom (as will be appreciated by the skilled person), a six
membered heterocyclic aromatic ring containing 1 heteroatom which
is an N atom, where the --N.dbd.N-- group is bonded to the
heterocyclic aromatic ring at the 2 position, a five membered
heterocyclic aromatic ring containing 1 heteroatom substituted with
an alkyl group selected from: an alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 8 carbon atoms, a straight
chain alkyl group having 8 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group having the formula:
##STR00017##
[0092] a six membered heterocyclic aromatic ring containing 1
heteroatom substituted with an alkyl group selected from: an alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 8 carbon atoms, a straight chain alkyl group having 8 carbon
atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula:
##STR00018##
or
[0093] a five membered heterocyclic aromatic ring having the
formula:
##STR00019##
[0094] Further, or in further examples where the dye compound is
according to Formula 1, one or more of the following apply: the
alkyl group of R.sup.d is selected from: a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group such that the alkoxy group of R.sup.9 has the
formula:
##STR00020##
or
[0095] the alkyl group of R.sup.e is selected from: a branched
alkyl group having 3 to 22 carbon atoms, a branched alkyl group
having 3 to 7 carbon atoms, a branched alkyl group having 7 carbon
atoms, or a branched alkyl group such that the amide group of
R.sup.9 has the formula:
##STR00021##
or
[0096] the alkyl group of R.sup.f is selected from: a branched
alkyl group having 3 to 22 carbon atoms, a branched alkyl group
having 3 to 8 carbon atoms, a branched alkyl group having 8 carbon
atoms, or a branched alkyl group having the formula:
##STR00022##
or
[0097] the alkyl group of R.sup.g is selected from: a straight
chain alkyl group having 1 to 22 carbon atoms, a straight chain
alkyl group having 2 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, a branched alkyl group having 3 to 8 carbon
atoms, a branched alkyl group having 8 carbon atoms, or a branched
alkyl group having the formula:
##STR00023##
[0098] Further, or in further examples with the dye compound
according to Formula 1, B has a formula selected from:
[0099] a formula where R.sup.12 is a cyano group having the formula
--CN, R.sup.13 is H, R.sup.14 is H and R.sup.15 is a cyano group
having the formula --CN, a formula where R.sup.12 is H, R.sup.13 is
H, R.sup.14 is H and R.sup.15 is a cyano group having the formula
--CN,
[0100] a formula where: R.sup.12 is an alkoxy group having the
formula --O--R.sup.h where R.sup.h is an alkyl group selected from:
a branched alkyl group having 3 to 22 carbon atoms, a branched
alkyl group having 3 to 8 carbon atoms, a branched alkyl group
having 8 carbon atoms, or a branched alkyl group having the
formula:
##STR00024##
[0101] R.sup.13 is H, R.sup.14 is an alkoxy group having the
formula --O--R.sup.k where R.sup.k is an alkyl group selected from:
a branched alkyl group having 3 to 22 carbon atoms, a branched
alkyl group having 3 to 8 carbon atoms, a branched alkyl group
having 8 carbon atoms, or a branched alkyl group having the
formula:
##STR00025##
[0102] R.sup.15 is a nitro group having the formula --NO.sub.2.
[0103] Further, or in further examples with the dye compound
according to Formula 1, A is selected from: a single bond, or where
A has the formula:
##STR00026##
or
[0104] the formula:
##STR00027##
[0105] R.sup.o and R.sup.p are independently selected from: a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a branched alkyl group having the formula:
##STR00028##
[0106] In an example of a dye compound according to Formula 1, the
dye compound has the following formula:
##STR00029##
[0107] This compound
N-(5-(bis(2-ethylhexyl)amino)-2-((E)-(4-((E)-4-cyanostyryl)-2,5-bis((2-et-
hylhexyl)oxy)phenyl)diazenyl)-4-((2-ethylhexyl)oxy)phenyl)-2-ethylhexanami-
de may be synthesised as follows:
##STR00030## ##STR00031##
1,4-bis((2-ethylhexyl)oxy)benzene
[0108] A mixture of hydroquinone (22.0 g, 0.20 mol), 2-ethylhexyl
bromide (90.0 g, 0.466 mol), potassium carbonate (60.0 g, 0.434
mol), 1.0 g tetrabutylammonium bromide and 100 mL 2-butanone was
heated under reflux for 24 h. The mixture was rotary evaporated and
the residue was stirred with 250 mL heptane, then filtered. The
same procedure was repeated. The filtrates were rotary evaporated
and the residue was purified by Kugelrohr distillation to give
49.25 g of 1,4-bis((2-ethylhexyl)oxy)benzene (0.147 mol, 74%).
2,5-bis((2-ethylhexyl)oxy)benzaldehyde
[0109] A mixture of 1,4-bis((2-ethylhexyl)oxy)benzene (32.08 g,
96.0 mmol) and dichloromethyl methyl ether (13.10 g, 0.114 mol) in
50 mL dichloromethane was added over a 75 min period to an
ice-cooled solution of tin(IV)chloride (27.1 g, 0.104 mol) in 45 mL
dichloromethane at 3-6.degree. C. The mixture was stirred for 2 h
in the ice-bath, then poured into 60 mL cold 6 N hydrochloric acid.
The layers were separated and the aqueous layer was extracted with
100 mL dichloromethane. The organic layers were stirred for 20 min
with ca. 20 mL some sodium carbonate in water, the layers were
separated, the organic layer was dried and rotary evaporated to
give 2,5-bis((2-ethylhexyl)oxy)benzaldehyde, which was used as such
in the next step.
(2,5-bis((2-ethylhexyl)oxy)phenyl)methylene diacetate
[0110] 2,5-Bis((2-ethylhexyl)oxy)benzaldehyde was dissolved in 70
mL acetic anhydride, the mixture was cooled in ice and 4 drops of
96% sulphuric acid were added (giving a temperature rise to
14.degree. C.). The mixture was stirred for 3 h, allowing the
temperature to rise to 16.degree. C. Sodium bicarbonate (5 g) was
added, the mixture was stirred for 5 min, 100 g ice was added, as
well as 100 mL heptane. The mixture was stirred for 10 min, then
the layers were separated (there was a small intermediate layer).
The two lower layers were extracted with 75 mL heptane. The heptane
layers were dried and rotary evaporated, then put under high vacuum
at 60.degree. C. to yield ca. 40 g of
(2,5-bis((2-ethylhexyl)oxy)phenyl)methylene diacetate, which was
used as such in the next step.
(2,5-bis((2-ethylhexyl)oxy)-4-nitrophenyl)methylene diacetate
[0111] A solution of (2,5-bis((2-ethylhexyl)oxy)phenyl)methylene
diacetate in 100 mL acetic anhydride was cooled in ice. Nitric acid
(90%; 12.10 g, 0.173 mol) was added over a 1 h period at
4-10.degree. C. The mixture was stirred for 1 h, allowing the
temperature to rise to 10.degree. C. 50 g ice was added, as well as
a suspension of 16 g sodium bicarbonate in 50 ml, water (addition
in portions) and 100 mL heptane. The mixture was stirred for 30
min, some more ice being added in order to keep the temperature
below 30.degree. C. The layers were separated and the aqueous layer
was extracted with 2.times.100 mL heptane containing some toluene.
The combined organic layers were stirred with 50 mL ice-water/5 g
sodium bicarbonate, the layers were separated, the organic layer
was dried and rotary evaporated to give 45.34 g (89.07 mmol, 93%
yield) of (2,5-bis((2-ethylhexyl)oxy)-4-nitrophenyl)methylene
diacetate, which was used as such in the next step.
2,5-bis((2-ethylhexyl)oxy)-4-nitrobenzaldehyde
[0112] (2,5-bis((2-ethylhexyl)oxy)-4-nitrophenyl)methylene
diacetate (29.64 g, 58.23 mmol) was dissolved in 125 mL ethanol. A
mixture of 6.6 g 96% sulphuric acid and 15 mL water was added and
the mixture was heated for 4 h at 70.degree. C. Most of the ethanol
was removed by rotary evaporation. 20 mL water was added and
extraction was performed with 2.times.150 mL TBME. The successive
organic layers were washed with 30 mL water, then dried and rotary
evaporated to yield 2,5-bis((2-ethylhexyl)oxy)-4-nitrobenzaldehyde
(21.54 g, 52.92 mmol, 91% yield) which was used as such in the next
step.
diethyl 4-cyanobenzylphosphonate
[0113] A mixture of 4-(chloromethyl)benzonitrile (9.10 g, 60.0
mmol), triethyl phosphite (35.0 g, 0.211 mol) and 10 mL toluene was
heated for 18 h at 135.degree. C. The mixture was rotary evaporated
and then heated under high vacuum to remove the last triethyl
phosphite. The residue, weighing 15.62 g, was used as such.
(E)-4-(2,5-bis((2-ethylhexyl)oxy)-4-nitrostyryl)benzonitrile
[0114] A solution of diethyl 4-cyanobenzylphosphonate (15.62 g,
65.84 mmol theor.), 2,5-bis((2-ethylhexyl)oxy)-4-nitrobenzaldehyde
(21.54 g, 52.92 mmol theor.) in 150 mL THF was cooled in ice.
Potassium t-butoxide (8.49 g, 75.8 mmol) in 100 mL THF was added in
ca. 30 min. The mixture was stirred overnight and rotary evaporated
at 55.degree. C. 100 mL water was added to the residue and
extraction was performed with 2.times.200 mL toluene. Washing with
25 mL water, drying and rotary evaporation yielded a residue which
was purified by chromatography on 140 g silica. Elution with
heptane, containing increasing amounts of toluene, yielded
(E)-4-(2,5-bis((2-ethylhexyl)oxy)-4-nitrostyryl)benzonitrile (17.55
g, 34.68 mmol, 66% yield) as a yellow solidifying oil.
(E)-4-(4-amino-2,5-bis((2-ethylhexyl)oxy)styryl)benzonitrile
[0115] (E)-4-(2,5-bis((2-ethylhexyl)oxy)-4-nitrostyryl)benzonitrile
(17.55 g, 34.68 mmol) was mixed with 250 mL ethanol and
tin(II)chloride dehydrate (40.0 g, 177.3 mmol). The mixture was
gradually warmed to 70.degree. C., and kept at that temperature for
1 h. Rotary evaporation was followed by addition of 200 mL water
and 200 mL TBME. An excess of sodium bicarbonate was added slowly
to the well-stirred mixture. The mixture was allowed to stand for 2
days, then the layers were separated and the aqueous layer (a
suspension) was extracted with 2.times.200 mL TBME. Drying and
rotary evaporation left a residue which was chromatographed on 117
g silica. Elution with heptane, containing increasing amounts of
toluene and ethyl acetate yielded
(E)-4-(4-amino-2,5-bis((2-ethylhexyl)oxy)styryl)benzonitrile (9.32
g, 19.58 mmol, 56% yield) as a pale-yellow oil.
N-(5-(bis(2-ethylhexyl)amino)-2-((E)-(4-((E)-4-cyanostyryl)-2,5-bis((2-eth-
ylhexyl)oxy)phenyl)diazenyl)-4-((2-ethylhexyl)oxy)phenyl)-2-ethylhexanamid-
e
[0116] (E)-4-(4-amino-2,5-bis((2-ethylhexyl)oxy)styryl)benzonitrile
(4.62 g, 9.71 mmol) was dissolved in 100 mL acetic acid and 20 mL
propionic acid. The solution was cooled in ice and nitrosylsulfuric
acid (40% solution in sulphuric acid; 3.12 g, 9.83 mmol) was added
slowly. After addition of some of the nitrosylsulfuric acid a thick
precipitate formed and the temperature rose to 8.degree. C. 25 mL
dioxane was added after some time, resulting in a solution and in a
temperature drop to 2.degree. C. The remainder of the
nitrosylsulfuric acid was added at 2-4.degree. C. in about 10
minutes. The dark red-brown solution was stirred for 20 min, then a
solution of the trialkylated amide 9 (7.80 g, 13.28 mmol; obtained
in 3 steps from 2-nitro-4-aminophenol via acylation, hydrogenation
and alkylation) in 25 mL dioxane was added over a 10 min period at
2-5.degree. C. The mixture was stirred for 30 min, allowing the
temperature to rise to 10.degree. C. The mixture was cooled with
ice and 15 mL 30% sodium hydroxide solution was added over a 30 min
period at 5-8.degree. C. The mixture was stirred for 16 h and then
poured into 150 mL toluene/100 mL water. The layers were separated,
the aqueous layer was extracted with 2.times.150 mL toluene and the
successive organic layers were washed with 50 mL water. Drying and
rotary evaporation yielded a residue which was purified by
chromatography.
[0117] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00032##
[0118] This compound
(E)-diethyl(2-((2,4-dicyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)amino-
)-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate may be synthesised as
follows:
##STR00033## ##STR00034## ##STR00035##
N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-5-nitroaniline
[0119] A mixture of 2-amino-4-nitrophenol (3.09 g, 20.0 mmol),
2-ethylhexyl bromide (20.3 g, 0.105 mol) and
N,N-diisopropylethylamine (13.0 g, 0.101 mol) was heated for 7 h at
134.degree. C. The mixture was cooled and worked up with water and
heptane. Drying, rotary evaporation and purification by column
chromatography over silica gave the N,O-dialkylated compound
N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-5-nitroaniline.
N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-N-hexyl-5-nitroaniline
[0120] N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-5-nitroaniline (25 g)
was heated for 7 d at 140.degree. C. with 1-bromohexane (40 mL,
0.284 mol), sodium carbonate (15.95 g, 0.150 mol) and 0.40 g
tetrabutylammonium bromide. The mixture was cooled and 50 mL water
was added. The mixture was extracted with 2.times.50 mL toluene.
Drying and rotary evaporation gave a residue which was
chromatographed on 100 g silica. Elution with heptane yielded the
product
N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-N-hexyl-5-nitroaniline (9.35
g).
N.sup.1-(2-ethylhexyl)-6-((2-ethylhexyl)oxy)-N.sup.1-hexylbenzene-1,3-diam-
ine
[0121] Hydrogenation of 18.70 g of
N-(2-ethylhexyl)-2-((2-ethylhexyl)oxy)-N-hexyl-5-nitroaniline in a
mixture of 250 mL THF and 20 mL acetic acid using 10% Pd/C as
catalyst gave, after filtration, rotary evaporation and heating at
80.degree. C. under high vacuum, a residue, which was heated under
reflux for 20 h with 10.0 g potassium hydroxide in 100 mL ethanol.
Rotary evaporation, addition of 75 mL water, extraction with
2.times.100 mL TBME, washing of the successive organic layers with
25 mL water, drying and rotary evaporation gave 8.67 g of
N.sup.1-(2-ethylhexyl)-6-((2-ethylhexyl)oxy)-N.sup.1-hexylbenzene-1,3-dia-
mine.
Diethyl(3-((2-ethylhexyl)(hexyl)amino)-4-((2-ethylhexyl)oxy)phenyl)phospho-
ramidate
[0122] To an ice-cooled mixture of 8.67 g
N.sup.1-(2-ethylhexyl)-6-((2-ethylhexyl)oxy)-N.sup.1-hexylbenzene-1,3-dia-
mine (20.03 mmol), 75 mL toluene and N,N-diisopropylethylamine
(12.95 g, 0.100 mol) was added diethyl chlorophosphate (7.35 g,
42.60 mmol) over a 20 min period. The mixture was stirred for 3 d
(days) at room temperature (RT), then warmed for 5 h at 80.degree.
C., before being cooled to RT. After addition of 50 mL of water and
10.0 g of sodium bicarbonate, the mixture was stirred for 30 min
and the layers were separated and extracted with 100 mL toluene.
Drying and rotary evaporation yielded a residue which was
chromatographed over 70 g silica, elution being done with heptane
containing increasing amounts of ethyl acetate yielding 4.40 g of
diethyl(3-((2-ethylhexyl)(hexyl)amino)-4-((2-ethylhexyl)oxy)phenyl)p-
hosphoramidate.
(E)-diethyl(2-((2-bromo-4-cyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)am-
ino)-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate
[0123] A mixture of 4-amino-3-bromobenzonitrile (2.07 g, 10.51
mmol), 25 mL acetic acid and 5 mL propionic acid was stirred for 15
min. The resulting solution was cooled in ice and nitrosylsulfuric
acid (40% solution in sulphuric acid; 3.32 g, 10.46 mmol) was added
over a 20 min period at 4-6.degree. C. The addition funnel was
flushed with 5 mL acetic acid, then the amide
diethyl(3-((2-ethylhexyl)(hexyl)amino)-4-((2-ethylhexyl)oxy)phenyl)phosph-
oramidate (4.40 g, 7.73 mmol), dissolved in 20 mL acetic acid, was
added over a 5 min period at 3-5.degree. C. The mixture was stirred
for 1 h, allowing the temperature to rise to 10.degree. C. The
resulting suspension was cooled with ice and 12 mL 30% sodium
hydroxide was added over a 15 min period at 8 to 16.degree. C. The
cooling bath was removed when the temperature had dropped to
10.degree. C. After stirring for 1 h there was added 25 mL dioxane
and the red-brown mixture was stirred for an additional hour at RT.
75 mL water was added and the mixture was extracted with
3.times.100 mL toluene, the successive organic layers being washed
with 50 mL water. Drying and rotary evaporation yielded a residue
which was purified by chromatography on 100 g silica. Elution with
heptane, containing increasing amounts of toluene and ethyl acetate
yielded the product
(E)-diethyl(2-((2-bromo-4-cyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)a-
mino)-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate as a red-magenta
oil.
(E)-diethyl(2-((2,4-dicyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)amino)-
-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate
[0124] The product
(E)-diethyl(2-((2-bromo-4-cyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)a-
mino)-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate was stirred for 8
h at 50.degree. C. with 25 mL dimethyl sulphoxide (DMSO) and
copper(I)cyanide (1.70 g, 19.0 mmol). The mixture was poured in 75
mL dilute ammonia and extraction was performed with 2.times.150 mL
toluene. The successive organic layers were washed with 30 mL
water, dried and rotary evaporated. The residue (2.20 g) was
chromatographed on 75 g silica, elution being done with heptane
containing increasing amounts of ethyl acetate. The product
fractions were combined to give the desired purple
(E)-diethyl(2-((2,4-dicyanophenyl)diazenyl)-5-((2-ethylhexyl)(hexyl)amino-
)-4-((2-ethylhexyl)oxy)phenyl)phosphoramidate.
[0125] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00036##
[0126] This compound is
N-{5-[bis(2-ethylhexyl)amino]-2-[(E)-2-(2,4-dicyanophenyl)diazen-1-yl]-4--
[(2-ethylhexyl)oxy]phenyl}-2-ethylhexane-1-sulfonamide.
[0127] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00037##
[0128] This compound is
4-[(E)-2-{4-[(E)-2-[1-(2-ethylhexyl)-1H-pyrrol-2-yl]diazen-1-yl]-2,5-bis[-
(2-ethylhexyl)oxy]phenyl}diazen-1-yl]benzonitrile.
[0129] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00038##
This compound
4-[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]phenyl]diazen-1-yl]-
benzene-1,3-dicarbonitrile may be synthesised as follows:
##STR00039## ##STR00040##
2,5-Bis((2-ethylhexyl)oxy)-N,N-dipentylaniline
[0130] 2,5-Bis((2-ethylhexyl)oxy)-aniline (5 g, 14.3 mmol, 1 eq)
was mixed with bromopentane (13 g, 86 mmol, 6 eq), K.sub.2CO.sub.3
(6 g, 43 mmol, 3 eq) and tetrabutylammoniumbromide (0.1 g). The
reaction mixture was stirred for 5 min at RT. The mixture was
heated to 100.degree. C. and stirred for 48 h. Temperature was
increased to 115.degree. C. and bromopentane (4.3 g, 29 mmol, 2 eq)
was added. After stirring for 71 h full conversion was obtained.
Reaction mixture was cooled to RT, mixed with EtOAc (50 mL), washed
with water (2.times.50 mL), dried (Na.sub.2SO.sub.4) and
concentrated. After distillation (Kugelrohr, 1 mbar, 100.degree.
C., 2 h, removal of bromopentane) the product
2,5-bis((2-ethylhexyl)oxy)-N,N-dipentylaniline (6.8 g, 97% isolated
yield) was obtained as a brown oil.
3-bromo-4
[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]phenyl]diaze-
n-1-yl]benzonitrile
[0131] 2-Bromo-4-cyanoaniline (3.8 g, 19.5 mmol, 1.4 eq) was mixed
with propionic acid (7.5 mL) and acetic acid (28 mL). The mixture
was stirred for 40 min. at room temperature and a yellow solution
was obtained. The solution was cooled to 0.degree. C.
Nitrosylsulfuric acid (6.2 g, 19.5 mmol, 1.4 eq, 40% sulfuric acid)
was added dropwise within 20 min. and the temperature was kept
between 0-3.degree. C. The clear yellow solution was added dropwise
to a solution of 2,5-bis((2-ethylhexyl)oxy)-N,N-dipentylaniline
(6.8 g, 13.0 mmol, 1 eq), 1.4 dioxane (45 mL) and acetic acid (9.5
mL) within 15 min. and the temperature was kept between 0-2.degree.
C. Stirring was continued for 2.5 h, and then the ice bath was
removed. While warming to room temperature the reaction was stirred
for another 1.5 h. Afterwards the mixture was cooled with an ice
bath and NaOH solution (NaOH, 33 w %, 10 mL, water 60 mL) was added
within 20 min. while the temperature was kept between 7-9.degree.
C. The mixture was stirred for 5 min. and poured into a solution of
toluene (200 mL) and water (100 mL). The organic layer was
separated, washed with water (50 mL). The aqueous layers were
combined, washed with toluene (3.times.100 mL). The organic layers
were combined, dried on Na.sub.2SO.sub.4, filtered and
concentrated. After purification by column chromatography
(silicagel, 10% EtOAc/heptane)
3-bromo-4-[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]phenyl]diaz-
en-1-yl]benzonitrile (4.6 g, 6.7 mmol, 51% yield) was isolated as a
red oil.
4-[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]phenyl]diazen-1-yl]b-
enzene-1,3-dicarbonitrile
[0132]
3-Bromo-4-[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]pheny-
l]diazen-1-yl]benzonitrile (3 g, 4.3 mmol, 1 eq) was dissolved in
DMF (50 mL). CuCN (967 mg) was added and the mixture was heated to
100.degree. C. The reaction mixture was cooled to RT and NH.sub.3
solution was added. The mixture was extracted with toluene
(3.times.60 mL), the organic layer was washed with water
(3.times.60 mL) and concentrated. The product was purified with
column chromatography (silicagel, 5% EtOAc/heptane) to afford
4-[(E)-2-[4-(dipentylamino)-2,5-bis[(2-ethylhexyl)oxy]phenyl]diaze-
n-1-yl]benzene-1,3-dicarbonitrile (800 mg, 29% yield) as a purple
solid.
[0133] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00041##
This compound is
N-{2-[(E)-2-{2,5-bis[(2-ethylhexyl)oxy]-4-nitrophenyl}diazen-1-yl]-5-(dib-
utylamino)-4-[(2-ethylhexyl)oxy]phenyl}-2-ethylhexanamide.
[0134] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00042##
[0135] This compound is
(E)-N-(5-(bis(2-ethylhexyl)amino)-2-((2,4-dicyanophenyl)diazenyl)-4-ethox-
yphenyl)-2-ethylhexanamide may be synthesised as follows:
##STR00043##
A suspension of 4-Amino-3-bromobenzonitrile (15.0 g, 76.1 mmol) in
a mixture of AcOH (120 mL) and EtCO.sub.2H (80 mL) was warmed until
a clear solution was obtained and then cooled to 8.degree. C. with
an ice bath. 40% nitrosyl sulfuric acid (14.3 mL, 83.7 mmol) was
added drop wise. The mixture was stirred 1 h at 7.degree. C. and
then added slowly to a solution of
N-{3-[bis(2-ethylhexyl)amino]-4-ethoxyphenyl}-2-ethylhexanamide
(35.0 g, 69.6 mmol) in 1,4-dioxane (120 mL) and acetic acid (30 mL)
cooled in an ice bath. The mixture was stirred at 7.degree. C.
during 1 h and then hydrolyzed by drop wise addition of 33% NaOH
(75 mL) while cooling in an ice bath. After 30 minutes, the mixture
was poured into water and extracted with toluene. The combined
organic layers were washed with water and the solvent evaporated.
Purification by column chromatography (silicagel, heptane/EtOAc
60/1) afforded
(E)-N-(5-(bis(2-ethylhexyl)amino)-2-((2-bromo-4-cyanophenyl)diazenyl)-4-e-
thoxyphenyl)-2-ethylhexanamide (35 g).
[0136] This was dissolved in dimethylformamide DMF (400 mL) and
copper(I) cyanide (17.6 g, 196.9 mmol) was added while the mixture
was cooled in a water bath. After 20 h of stirring at RT, the
reaction mixture was poured into 15% ammonia and extracted with
toluene (3.times.). The combined organic layers were washed with
ammonia, water and dried with Na.sub.2SO.sub.4. After evaporation
of the solvent the residue was purified by column chromatography
(silicagel, heptane/EtOAc 80/1 to 30/1) to obtain
(E)-N-(5-(bis(2-ethylhexyl)amino)-2-((2,4-dicyanophenyl)diazeny-
l)-4-ethoxyphenyl)-2-ethylhexanamide (19.8 g, 39% yield) as a
purple oil.
[0137] In another example of a dye compound according to Formula 1,
the dye compound has the following formula:
##STR00044##
In a further example of a dye compound according to Formula 1, the
dye compound has the following formula:
##STR00045##
[0138] In further examples, the fluid for an electrowetting
apparatus, such as that described above, includes at least one dye
compound having the following formula:
##STR00046##
[0139] where R30 is selected from: OH, or an amino group having the
formula --N(R.sup.q)(R.sup.r), with R.sup.q being H and R.sup.r
being an alkyl group (such a secondary amino group gives greater
solubility in the carrier fluid compared with a primary amine and a
greater stability and colour intensity than a tertiary amino
group); an alkoxy group having the formula --O--R.sup.ae, with
R.sup.ae being an alkyl group; or a thioalkyl group having the
formula --S--R.sup.af, with R.sup.af being an alkyl group, R31 is
selected from: H, or has the formula --X--Y, where X is selected
from: --S--, a single bond, or --O--; Y is selected from:
--R.sup.s, or --R.sup.A, where R.sup.s is an alkyl group and
R.sup.A is an aryl group; R.sup.32 is H; R.sup.33 is selected from:
an amino group having the formula --N(R.sup.t)(R.sup.u), with
R.sup.t being H and Ru being an alkyl group (such a secondary amino
group has similar benefits as the amino group of R.sup.30), an
alkoxy group having the formula --O--R.sup.af, with R.sup.af being
an alkyl group, or a thioalkyl group having the formula
--S--R.sup.ag, with R.sup.ag being an alkyl group; R.sup.34 and
R.sup.35 are selected from the following: R.sup.34 and R.sup.35 are
each H, or together R.sup.34 and R.sup.35 form:
##STR00047##
[0140] where R.sup.36, R.sup.38 and R.sup.39 are each independently
selected from: H, or an alkyl group; R.sup.37 is selected from: H,
an alkyl group, or an ester group having the formula
--COO--R.sup.ah, where R.sup.ah is an alkyl group [0141] In
examples, the alkyl group of one or more of: R.sup.q, R.sup.r,
R.sup.ae, R.sup.af, R.sup.s, R.sup.t, R.sup.u, R.sup.af, R.sup.ag,
R.sup.36, R.sup.38, R.sup.39, R.sup.37, R.sup.ah, is independently
selected from: a straight chain alkyl group having 1 to 22 carbon
atoms, a branched alkyl group having 3 to 22 carbon atoms, or a
cyclic alkyl group having 5 to 22 carbon atoms. Further, or in
further examples where the dye compound is according to Formula 2,
the dye compound is selected from:
[0142] a formula where: R.sup.30 is OH, R31 has the formula --X--Y
where X is a single bond and Y is --R.sup.s where --R.sup.s is
selected from: an alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 22 carbon atoms, a straight
chain alkyl group having 1 to 8 carbon atoms, a straight chain
alkyl group having 8 carbon atoms, a branched alkyl group having 3
to 22 carbon atoms, a branched alkyl group having 3 to 8 carbon
atoms, a branched alkyl group having 8 carbon atoms, or a branched
alkyl group having the formula:
##STR00048##
[0143] R.sup.33 is the amino group having the formula
--N(R.sup.t)(R.sup.u), with R.sup.t being H and R.sup.u being an
alkyl group selected from: an alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 8 carbon atoms, a straight
chain alkyl group having 8 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group having the formula:
##STR00049##
[0144] R.sup.34 and R.sup.35 together form:
##STR00050##
[0145] where R.sup.36, R.sup.37, R.sup.38 and R.sup.39 are each H,
or
[0146] a formula where: R.sup.30 is the amino group having the
formula --N(R.sup.q)(R.sup.r), with R.sup.q being H and R.sup.r
being an alkyl group selected from: an alkyl group having 1 to 22
carbon atoms, a straight chain alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 8 carbon atoms, a
straight chain alkyl group having 8 carbon atoms, a branched alkyl
group having 3 to 22 carbon atoms, a branched alkyl group having 3
to 8 carbon atoms, a branched alkyl group having 8 carbon atoms, or
a methyl alkyl group; R.sup.31 has the formula --X--Y where X is
--S-- and Y is R.sup.s being an alkyl group selected from: an alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 12 carbon atoms, a straight chain alkyl group having 12 carbon
atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 12 carbon atoms, a branched alkyl
group having 12 carbon atoms, or a branched alkyl group having the
formula:
##STR00051##
[0147] R.sup.33 is the amino group having the formula
--N(R.sup.t)(R.sup.u), with R.sup.t being H and R.sup.u being an
alkyl group selected from: an alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 8 carbon atoms, a straight
chain alkyl group having 8 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group having the formula:
##STR00052##
[0148] R.sup.34 and R.sup.35 together form:
##STR00053##
[0149] where R.sup.36, R.sup.37, R.sup.38 and R.sup.39 are each
H.
[0150] In an example of a dye compound according to Formula 2, the
dye compound has the following formula:
##STR00054##
[0151] This compound is
4-[(2-ethylhexyl)amino]-1-(methylamino)-2-[(2-methylundecan-2-yl)sulfanyl-
]-9,10-dihydroanthracene-9,10-dione.
[0152] In another example of a dye compound according to Formula 2,
the dye compound has the following formula:
##STR00055##
[0153] This compound
2-(2-ethylhexyl)-4-[(2-ethylhexyl)amino]-1-hydroxy-9,10-dihydroanthracene-
-9,10-dione may be synthesised as follows:
[0154] 346 g of leucoquinizarin was reacted with 186 g of
2-ethylhexylamine in dichloromethane. After stirring for 24 h, the
mixture was rotary evaporated and 520 g of 2-ethylhexanal in
isopropanol was added to the residual imine with cooling, followed
by addition of 316 g piperidinium acetate in isopropanol. After
stirring for 48 h at 70 to 85.degree. C., the mixture was worked up
and the crude product was chromatographed. This resulted in a total
yield of 336 g of the desired product
2-(2-ethylhexyl)-4-[(2-ethylhexyl)amino]-1-hydroxy-9,10-dihydroan-
thracene-9,10-dione (51% yield).
[0155] In further examples, the fluid for an electrowetting
apparatus, such as that described above, includes at least one dye
compound having the following formula:
##STR00056##
where each of R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45, R.sup.46 is independently selected from: H, an alkoxy
group, an alkyl group, or an amino group having the formula
--N(R.sup.v)(R.sup.w), with each of R.sup.v and R.sup.w
independently being an alkyl group for a tertiary amino group or
one of R.sup.v and R.sup.w being H and the other one of R.sup.v and
R.sup.w being an alkyl group for a secondary amino group (a primary
amino group is not sufficiently soluble in the carrier fluid);
where R.sup.47 is an arylene group and R.sup.48 is an aryl
group.
[0156] In examples, the alkyl group of one or more of: R.sup.40,
R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46,
R.sup.y, R.sup.w is independently selected from: a straight chain
alkyl group having 1 to 22 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, or a cyclic alkyl group having 5 to 22
carbon atoms.
[0157] Further, or in further examples where the dye compound is
according to Formula 3, R.sup.4, R.sup.41, R.sup.42, R.sup.43,
R.sup.44, R.sup.45, R.sup.46 are each independently selected from:
H, a straight chain alkyl group having 1 to 22 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, or an amino group
having the formula --N(R.sup.v)(R.sup.w), with each of R.sup.v and
R.sup.w independently being selected from: H, or an alkyl group
selected from: a straight chain alkyl group having 1 to 22 carbon
atoms, or a branched alkyl group having 3 to 22 carbon atoms;
R.sup.47 has the formula:
##STR00057##
[0158] where each of R.sup.am, R.sup.an, R.sup.ao, R.sup.ap is
independently selected from: H, a straight chain alkyl group having
1 to 22 carbon atoms, or a branched alkyl group having 3 to 22
carbon atoms; R.sup.48 has the formula:
##STR00058##
where each of R.sup.aq, R.sup.ar, R.sup.at, is independently
selected from: H, a straight chain alkyl group having 1 to 22
carbon atoms, a halogen atom, or a branched alkyl group having 3 to
22 carbon atoms, wherein R.sup.as is selected from: H, a straight
chain alkyl group having 1 to 22 carbon atoms, a halogen atom, an
ester group, or a branched alkyl group having 3 to 22 carbon atoms,
wherein R.sup.au is selected from: H, a straight chain alkyl group
having 3 to 22 carbon atoms, a halogen atom, a cyano group, a nitro
group, or a branched alkyl group having 3 to 22 carbon atoms.
[0159] In further examples, the fluid for an electrowetting
apparatus, such as that described above, includes at least one dye
compound having the following formula:
##STR00059##
[0160] where R.sup.50 and R.sup.51 are independently selected from:
H, or an amide group having the formula --NH--C(.dbd.O)R.sup.aj
with R.sup.aj being selected from H, or an alkyl group, or together
R.sup.50 and R.sup.51 form:
##STR00060##
[0161] where each of R.sup.60, R.sup.61, R.sup.62, R.sup.63 is
independently H or an alkyl group; R.sup.53 and R.sup.54 are
selected from the following: R.sup.53 and R.sup.54 are each H, or
together R.sup.53 and R.sup.54 form:
##STR00061##
[0162] where each of R.sup.64, R.sup.65, R.sup.66, R.sup.67 is
independently H or an alkyl group; R.sup.52 has the formula:
##STR00062##
[0163] where R.sup.55 is selected from: an alkoxy group having the
formula --O--R.sup.x, where R.sup.x is an alkyl group, an alkyl
group, or a halogen atom; R.sup.57 is an amino group having the
formula --N(R.sup.y)(R.sup.z), with each of R.sup.y and R.sup.z
independently being selected from: H, or an alkyl group; each of
R.sup.56, R.sup.58 and R.sup.59 is independently selected from: H,
or an alkyl group.
[0164] In examples, the alkyl group of one or more of: R.sup.aj,
R.sup.ak, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64,
R.sup.65, R.sup.66, R.sup.67, R.sup.x, R.sup.55, R.sup.y, R.sup.z,
R.sup.56, R.sup.58, or R.sup.59 is independently selected from: a
straight chain alkyl group having 1 to 22 carbon atoms, a branched
alkyl group having 3 to 22 carbon atoms, or a cyclic alkyl group
having 5 to 22 carbon atoms.
[0165] Further, or in further examples where the dye compound is
according to Formula 4, R.sup.50 and R.sup.51 are each H, R.sup.53
and R.sup.54 together form:
##STR00063##
[0166] where each of R.sup.64, R.sup.65, R.sup.66, R.sup.67 is H,
and R.sup.52 has the formula:
##STR00064##
[0167] where R.sup.55 is the alkoxy group having the formula
--O--R.sup.x, where R.sup.x is an alkyl group selected from: an
alkyl group having 1 to 22 carbon atoms, a straight chain alkyl
group having 1 to 22 carbon atoms, a straight chain alkyl group
having 1 to 8 carbon atoms, a straight chain alkyl group having 8
carbon atoms, a branched alkyl group having 3 to 22 carbon atoms, a
branched alkyl group having 3 to 8 carbon atoms, a branched alkyl
group having 8 carbon atoms, or a branched alkyl group having the
formula:
##STR00065##
[0168] R.sup.56, R.sup.58 and R.sup.59 are H, and R.sup.57 is the
amino group having the formula --N(R.sup.y)(R.sup.z), with each of
R.sup.y and R.sup.z independently being selected from: H, or an
alkyl group selected from: an alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 8 carbon atoms, a straight
chain alkyl group having 8 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, or a
branched alkyl group having the formula:
##STR00066##
[0169] Further, or in further examples where the dye compound is
according to Formula 4, the dye compound is selected from:
[0170] a formula where R.sup.50, R.sup.51, R.sup.53 are each H;
R.sup.54 is the amide group having the formula
--NH--C(.dbd.O)(R.sup.aj) with R.sup.aj being selected from H, or
an alkyl group selected from: an alkyl group having 1 to 22 carbon
atoms, a straight chain alkyl group having 1 to 22 carbon atoms, a
straight chain alkyl group having 1 to 8 carbon atoms, a straight
chain alkyl group having 8 carbon atoms, a branched alkyl group
having 3 to 22 carbon atoms, a branched alkyl group having 3 to 8
carbon atoms, a branched alkyl group having 8 carbon atoms, a
methyl group, or a branched alkyl group having the formula:
##STR00067##
R.sup.55 is an alkyl group selected from: an alkyl group having 1
to 22 carbon atoms, a straight chain alkyl group having 1 to 22
carbon atoms, a straight chain alkyl group having 1 to 8 carbon
atoms, a straight chain alkyl group having 8 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a methyl group; R.sup.56, R.sup.58 and R.sup.59
are H; R.sup.57 is an alkyl group selected from: an alkyl group
having 1 to 22 carbon atoms, a straight chain alkyl group having 1
to 22 carbon atoms, a straight chain alkyl group having 1 to 8
carbon atoms, a straight chain alkyl group having 8 carbon atoms, a
branched alkyl group having 3 to 22 carbon atoms, a branched alkyl
group having 3 to 8 carbon atoms, a branched alkyl group having 8
carbon atoms, or a branched alkyl group having the formula:
##STR00068##
[0171] In an example of a dye compound according to Formula 4, the
dye compound has the following formula:
##STR00069##
This compound
N-[3-({4-[bis(2-ethylhexyl)amino]-2-methylphenyl}imino)-6-oxocyclohexa-1,-
4-dien-1-yl]acetamide may be synthesised as follows:
##STR00070##
N,N-bis(2-ethylhexyl)-3-methylaniline
[0172] A mixture of 3-methylaniline (10.70 g, 0.100 mol),
2-ethylhexyl bromide (81.0 g, 0.420 mol) and potassium carbonate
(40.0 g, 0.290 mol) was heated for 3 d at 105.degree. C. and 10 d
at 122.degree. C. Additional potassium carbonate (10.0 g) and
2-ethylhexyl bromide (20 mL) were added and heating was continued
for 3 d. After cooling, 150 mL heptane was added and the mixture
was filtered and washed with heptane. Rotary evaporation of the
filtrate, followed by Kugelrohr distillation gave a fraction which
contained a considerable amount of the monoalkyl compound, followed
by 7.14 g of the dialkyl compound
N,N-bis(2-ethylhexyl)-3-methylaniline.
N,N-bis(2-ethylhexyl)-3-methylbenzene-1,4-diamine
[0173] A solution of sodium nitrite (3.45 g, 50.0 mmol) in 10 mL
water was added over a 20 min period and at 4-8.degree. C. to an
ice-cooled solution of N,N-bis(2-ethylhexyl)-3-methylaniline (15.15
g, 45.7 mmol) in 30 mL acetic acid and 20 mL conc. hydrochloric
acid. The mixture was stirred for 45 min in the cold bath and then
it was poured in 100 mL water. The product was extracted with
2.times.150 mL toluene/dichloromethane (6/1). The successive
organic layers were washed with 75 mL water, dried and rotary
evaporated.
[0174] The residue was dissolved in 150 mL THF, the solution was
cooled with ice and lithium aluminium hydride (3.0 g, 88.2 mmol)
was added in small portions. The mixture was heated under reflux
for 2 h after addition of the hydride. An additional 1.0 g lithium
aluminium hydride was added and reflux was continued for 11/2 h.
After stirring overnight, the mixture was slowly treated with 10 mL
33% sodium hydroxide solution. Some sodium sulphate was added, the
mixture was stirred for 15 min, filtered and washed with THF. The
filtrate was rotary evaporated and the residue was used as such in
the next step.
N-[3-({4-[bis(2-ethylhexyl)amino]-2-methylphenyl}imino)-6-oxocyclohexa-1,4-
-dien-1-yl]acetamide
[0175] Sodium bicarbonate (3.60 g, 42.86 mmol) was added to a
solution of 2-acetamidophenol (1.59 g, 10.53 mmol) in 100 mL ethyl
acetate and 25 mL ethanol, followed by 15 mL water. The mixture was
stirred for 5 min, then
N,N-bis(2-ethylhexyl)-3-methylbenzene-1,4-diamine (5.50 g, 15.9
mmol if pure) was added. The mixture was cooled in ice and a
solution of potassium hexacyanoferrate (14.15 g, 42.98 mmol) in 60
mL water was added over a 15 min period at 2-8.degree. C. The
cooling bath was removed after 5 min and the greenish mixture was
stirred for 40 min (internal temperature reached 14.degree. C.).
The mixture was poured in 50 mL water and extracted with
2.times.150 mL heptane/ethyl acetate. The successive organic layers
were washed with 50 mL water, dried and rotary evaporated. The
residue was chromatographed on 50 g silicagel, elution being done
with heptane containing increasing amounts of ethyl acetate. The
blue fractions were checked for purity by TLC and the pure
fractions were combined to yield 1.13 g of
N-[3-({4-[bis(2-ethylhexyl)amino]-2-methylphenyl}imino)-6-oxocyclohexa-1,-
4-dien-1-yl]acetamide as a solidifying blue oil.
[0176] The above examples are to be understood as illustrative
examples. Further examples are envisaged. It is to be understood
that any feature described in relation to any one example may be
used alone, or in combination with other features described, and
may also be used in combination with one or more features of any
other of the examples, or any combination of any other of the
examples. Furthermore, equivalents and modifications not described
above may also be employed without departing from the scope of the
accompanying claims.
* * * * *